Chromium-Catalyzed Production of Alcohols From Hydrocarbons

ABSTRACT

Processes for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound are disclosed, and these processes include the steps of forming a supported chromium catalyst comprising chromium in a hexavalent oxidation state, irradiating the hydrocarbon reactant and the supported chromium catalyst with a light beam at a wavelength in the UV-visible spectrum to reduce at least a portion of the supported chromium catalyst to form a reduced chromium catalyst, and hydrolyzing the reduced chromium catalyst to form a reaction product comprising the alcohol compound and/or the carbonyl compound. The supported chromium catalyst can be formed by heat treating a supported chromium precursor, contacting a chromium precursor with a solid support while heat treating, or heat treating a solid support and then contacting a chromium precursor with the solid support.

REFERENCE TO RELATED APPLICATION

This application claims the benefit of U.S. Provisional PatentApplication No. 62/900,687, filed on Sep. 16, 2019, the disclosure ofwhich is incorporated herein by reference in its entirety.

FIELD OF THE INVENTION

The present disclosure generally relates to methods for convertinghydrocarbons into alcohols and/or carbonyls, and more particularly,relates to performing such methods with a supported chromium catalyst.

BACKGROUND OF THE INVENTION

Alcohol compounds can be prepared by various synthesis techniques fromalkanes, but such techniques often require halogens or harsh reactionconditions. Alternative reaction schemes are therefore desirable.Accordingly, it is to these ends that the present invention is generallydirected.

SUMMARY OF THE INVENTION

This summary is provided to introduce a selection of concepts in asimplified form that are further described below in the detaileddescription. This summary is not intended to identify required oressential features of the claimed subject matter. Nor is this summaryintended to be used to limit the scope of the claimed subject matter.

Aspects of this invention are directed to processes for converting ahydrocarbon reactant into an alcohol compound and/or a carbonylcompound, and such processes can comprise (a)(i) heat treating asupported chromium precursor at a peak temperature from about 50° C. toabout 1000° C. to form a supported chromium catalyst comprising chromiumin a hexavalent oxidation state, or (a)(ii) contacting a chromiumprecursor with a solid support while heat treating at a peak temperaturefrom about 50° C. to about 1000° C. to form a supported chromiumcatalyst comprising chromium in a hexavalent oxidation state, or(a)(iii) heat treating a solid support at a peak temperature from about50° C. to about 1000° C. and then contacting a chromium precursor withthe solid support to form a supported chromium catalyst comprisingchromium in a hexavalent oxidation state, (b) irradiating thehydrocarbon reactant and the supported chromium catalyst with a lightbeam at a wavelength in the UV-visible spectrum to reduce at least aportion of the supported chromium catalyst to form a reduced chromiumcatalyst, and (c) hydrolyzing the reduced chromium catalyst to form areaction product comprising the alcohol compound and/or the carbonylcompound. Optionally, these processes can further comprise a step ofcalcining all or a portion of the reduced chromium catalyst toregenerate the supported chromium catalyst.

In step (b), at least a portion of the chromium on the reduced chromiumcatalyst can have at least one bonding site with a hydrocarboxy group (a—O-hydrocarbon group), which upon hydrolysis in step (c), can release analcohol compound and/or carbonyl compound analog of the hydrocarboncompound. For instance, if the hydrocarbon is cyclohexane (or methane),then the alcohol compound can be cyclohexanol (or methanol).

Both the foregoing summary and the following detailed descriptionprovide examples and are explanatory only. Accordingly, the foregoingsummary and the following detailed description should not be consideredto be restrictive. Further, features or variations may be provided inaddition to those set forth herein. For example, certain aspects may bedirected to various feature combinations and sub-combinations describedin the detailed description.

Definitions

To define more clearly the terms used herein, the following definitionsare provided. Unless otherwise indicated, the following definitions areapplicable to this disclosure. If a term is used in this disclosure butis not specifically defined herein, the definition from the IUPACCompendium of Chemical Terminology, 2^(nd) Ed (1997), can be applied, aslong as that definition does not conflict with any other disclosure ordefinition applied herein, or render indefinite or non-enabled any claimto which that definition is applied. To the extent that any definitionor usage provided by any document incorporated herein by referenceconflicts with the definition or usage provided herein, the definitionor usage provided herein controls.

Herein, features of the subject matter are described such that, withinparticular aspects, a combination of different features can beenvisioned. For each and every aspect and each and every featuredisclosed herein, all combinations that do not detrimentally affect thecatalysts, compositions, processes, or methods described herein arecontemplated with or without explicit description of the particularcombination. Additionally, unless explicitly recited otherwise, anyaspect or feature disclosed herein can be combined to describe inventivecatalysts, compositions, processes, or methods consistent with thepresent disclosure.

Generally, groups of elements are indicated using the numbering schemeindicated in the version of the periodic table of elements published inChemical and Engineering News, 63(5), 27, 1985. In some instances, agroup of elements can be indicated using a common name assigned to thegroup; for example, alkali metals for Group 1 elements, alkaline earthmetals for Group 2 elements, transition metals for Group 3-12 elements,and halogens or halides for Group 17 elements.

The term “hydrocarbon” whenever used in this specification and claimsrefers to a compound containing only carbon and hydrogen, whethersaturated or unsaturated. Other identifiers can be utilized to indicatethe presence of particular groups in the hydrocarbon (e.g., halogenatedhydrocarbon indicates the presence of one or more halogen atomsreplacing an equivalent number of hydrogen atoms in the hydrocarbon).Non-limiting examples of hydrocarbons include alkanes (linear, branched,and cyclic), alkenes (olefins), and aromatics, among other compounds.Herein, cyclics and aromatics encompass fused ring compounds such asbicyclics and polycyclics.

For any particular compound or group disclosed herein, any name orstructure (general or specific) presented is intended to encompass allconformational isomers, regioisomers, stereoisomers, and mixturesthereof that can arise from a particular set of substituents, unlessotherwise specified. The name or structure (general or specific) alsoencompasses all enantiomers, diastereomers, and other optical isomers(if there are any) whether in enantiomeric or racemic forms, as well asmixtures of stereoisomers, as would be recognized by a skilled artisan,unless otherwise specified. For instance, a general reference to pentaneincludes n-pentane, 2-methyl-butane, and 2,2-dimethylpropane; and ageneral reference to a butyl group includes a n-butyl group, a sec-butylgroup, an iso-butyl group, and a t-butyl group.

Unless otherwise specified, the term “substituted” when used to describea group, for example, when referring to a substituted analog of aparticular group, is intended to describe any non-hydrogen moiety thatformally replaces a hydrogen in that group, and is intended to benon-limiting. Also, unless otherwise specified, a group or groups canalso be referred to herein as “unsubstituted” or by equivalent termssuch as “non-substituted,” which refers to the original group in which anon-hydrogen moiety does not replace a hydrogen within that group.Moreover, unless otherwise specified, “substituted” is intended to benon-limiting and include inorganic substituents or organic substituentsas understood by one of ordinary skill in the art.

The terms “contacting” and “combining” are used herein to describecatalysts, compositions, processes, and methods in which the materialsor components are contacted or combined together in any order, in anymanner, and for any length of time, unless otherwise specified. Forexample, the materials or components can be blended, mixed, slurried,dissolved, reacted, treated, impregnated, compounded, or otherwisecontacted or combined in some other manner or by any suitable method ortechnique.

“BET surface area” as used herein means the surface area as determinedby the nitrogen adsorption Brunauer, Emmett, and Teller (BET) methodaccording to ASTM D1993-91, and as described, for example, in Brunauer,S., Emmett, P. H., and Teller, E., “Adsorption of gases inmultimolecular layers,” J. Am. Chem. Soc., 60, 3, pp. 309-319, thecontents of which are expressly incorporated by reference herein.

In this disclosure, while catalysts, compositions, processes, andmethods are described in terms of “comprising” various components orsteps, the catalysts, compositions, processes, and methods also can“consist essentially of” or “consist of” the various components orsteps, unless stated otherwise.

The terms “a,” “an,” and “the” are intended to include pluralalternatives, e.g., at least one. For instance, the disclosure of “ahydrocarbon reactant,” “a solid oxide,” etc., is meant to encompass one,or mixtures or combinations of more than one, hydrocarbon reactant,solid oxide, etc., unless otherwise specified.

Several types of ranges are disclosed in the present invention. When arange of any type is disclosed or claimed, the intent is to disclose orclaim individually each possible number that such a range couldreasonably encompass, including end points of the range as well as anysub-ranges and combinations of sub-ranges encompassed therein. Forexample, when a chemical compound having a certain number of carbonatoms is disclosed or claimed, the intent is to disclose or claimindividually every possible number that such a range could encompass,consistent with the disclosure herein. For example, the disclosure thata hydrocarbon reactant contains a C₁ to C₁₈ alkane compound, or inalternative language, an alkane compound having from 1 to 18 carbonatoms, as used herein, refers to a compound that can have 1, 2, 3, 4, 5,6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, or 18 carbon atoms, as wellas any range between these two numbers (for example, a C₁ to C₈ alkanecompound), and also including any combination of ranges between thesetwo numbers (for example, a C₂ to C₄ alkane compound and a C₁₂ to C₁₆alkane compound).

Similarly, another representative example follows for the amount ofchromium on the supported chromium catalyst consistent with aspects ofthis invention. By a disclosure that the amount of chromium can be in arange from about 0.1 to about 15 wt. %, the intent is to recite that theamount of chromium can be any amount in the range and, for example, canbe equal to about 0.1, about 0.2, about 0.3, about 0.4, about 0.5, about0.6, about 0.7, about 0.8, about 0.9, about 1, about 2, about 3, about4, about 5, about 6, about 7, about 8, about 9, about 10, about 11,about 12, about 13, about 14, or about 15 wt. %. Additionally, theamount of chromium can be within any range from about 0.1 to about 15wt. % (for example, from about 0.1 to about 5 wt. %), and this alsoincludes any combination of ranges between about 0.1 and about 15 wt. %(for example, the amount of chromium can be in a range from about 0.5 toabout 2.5 wt. %, or from about 5 to about 15 wt. %). Further, in allinstances, where “about” a particular value is disclosed, then thatvalue itself is disclosed. Thus, the disclosure that the amount ofchromium can be from about 0.1 to about 15 wt. % also discloses anamount of chromium from 0.1 to 15 wt. % (for example, from 0.1 to 5 wt.%), and this also includes any combination of ranges between 0.1 and 15wt. % (for example, the amount of chromium can be in a range from 0.5 to2.5 wt. %, or from 5 to 15 wt. %). Likewise, all other ranges disclosedherein should be interpreted in a manner similar to these examples.

The term “about” means that amounts, sizes, formulations, parameters,and other quantities and characteristics are not and need not be exact,but can be approximate including being larger or smaller, as desired,reflecting tolerances, conversion factors, rounding off, measurementerrors, and the like, and other factors known to those of skill in theart. In general, an amount, size, formulation, parameter or otherquantity or characteristic is “about” or “approximate” whether or notexpressly stated to be such. The term “about” also encompasses amountsthat differ due to different equilibrium conditions for a compositionresulting from a particular initial mixture. Whether or not modified bythe term “about,” the claims include equivalents to the quantities. Theterm “about” can mean within 10% of the reported numerical value, andoften within 5% of the reported numerical value.

Although any methods, devices, and materials similar or equivalent tothose described herein can be used in the practice or testing of theinvention, the typical methods, devices, and materials are hereindescribed.

All publications and patents mentioned herein are incorporated herein byreference for the purpose of describing and disclosing, for example, theconstructs and methodologies that are described in the publications,which might be used in connection with the presently describedinvention.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is generally directed to the conversion of ahydrocarbon into an analogous alcohol compound and/or carbonyl compound.Unexpectedly, it was found that the combined use of a supported chromiumcatalyst, light reduction, and hydrolysis can efficiently convert thehydrocarbon (e.g., an alkane) into the analogous alcohol compound and/orcarbonyl compound, and beneficially, even at ambient temperature.

Unexpectedly, it was also found that the high calcination/activationtemperatures that are generally required for supported chromiumpolymerization catalysts—such as 600-900° C.—are not necessary toproduce alcohols and/or carbonyls as described herein. Whereascalcination below these traditional high temperatures results in a pooror inactive supported chromium polymerization catalyst, heat treatmenttemperatures in the 100-500° C. range were effective to remove freewater and/or dry the supported catalyst and/or convert or stabilize thechromium (VI), thereby efficiently producing desirable alcohol and/orcarbonyl products.

Also unexpectedly, chromate compounds—such as potassium chromate,potassium dichromate, and the like—which are completely ineffective foruse in polymerization catalysts, were very efficient catalysts forconverting hydrocarbons into alcohols and/or carbonyls. Andbeneficially, very low heat treatment temperatures can be used, sincechromium (VI) is already present.

Generally, supported chromium polymerization catalysts are limited toloadings of chromium of about 1 wt. %. When the chromium (VI) isstabilized by binding to the silica or other support, the loading cannotbe too high, or the chromium can degrade into unusable chromium (III).However, and beneficially, high chromium loadings of 5-10 wt. %, andeven 20-50 wt. %, can easily be utilized in the process describedherein, and these higher loadings result in higher overall yields of thealcohol and/or carbonyl products (more chromium equals more product).Conversely, it was also found that low chromium loadings, such as lessthan 0.5 wt. %, can be highly selective to desirable alcohol and/orcarbonyl products, although they are not very active for polymerization.

Processes for Converting Hydrocarbons into Alcohols

Disclosed herein are processes for converting a hydrocarbon reactantinto an alcohol compound and/or a carbonyl compound. These processes cancomprise (a)(i) heat treating a supported chromium precursor at a peaktemperature from about 50° C. to about 1000° C. to form a supportedchromium catalyst comprising chromium in a hexavalent oxidation state,or (a)(ii) contacting a chromium precursor with a solid support whileheat treating at a peak temperature from about 50° C. to about 1000° C.to form a supported chromium catalyst comprising chromium in ahexavalent oxidation state, or (a)(iii) heat treating a solid support ata peak temperature from about 50° C. to about 1000° C. and thencontacting a chromium precursor with the solid support to form asupported chromium catalyst comprising chromium in a hexavalentoxidation state, (b) irradiating the hydrocarbon reactant and thesupported chromium catalyst with a light beam at a wavelength in theUV-visible spectrum to reduce at least a portion of the supportedchromium catalyst to form a reduced chromium catalyst, and (c)hydrolyzing the reduced chromium catalyst to form a reaction productcomprising the alcohol compound and/or the carbonyl compound. While notwishing to be bound by theory, it is believed that in step (b), at leasta portion of the chromium on the reduced chromium catalyst can have atleast one bonding site with a hydrocarboxy group (a —O-hydrocarbongroup) such as an alkoxy group, which upon hydrolysis in step (c), canrelease an alcohol compound and/or carbonyl compound analog of thehydrocarbon compound. The reduced chromium catalyst has an averageoxidation state less than that of the supported chromium catalyst.

Generally, the features of this process (e.g., the chromium precursor,the supported chromium precursor, the peak temperature, the hydrocarbonreactant, the supported chromium catalyst, the reduced chromiumcatalyst, the light beam, and the conditions under which the irradiatingstep and the hydrolyzing step are conducted, among others) areindependently described herein and these features can be combined in anycombination to further describe the disclosed processes to producealcohol compounds and/or carbonyl compounds. Moreover, additionalprocess steps can be performed before, during, and/or after any of thesteps in any of the processes disclosed herein, and can be utilizedwithout limitation and in any combination to further describe theseprocesses, unless stated otherwise. Further, any alcohol compoundsand/or carbonyl compounds produced in accordance with the disclosedprocesses are within the scope of this disclosure and are encompassedherein.

Referring first to step (a)(i), a supported chromium precursor can beheat treated at a peak temperature from about 50° C. to about 1000° C.to form the supported chromium catalyst comprising chromium in ahexavalent oxidation state. The supported chromium precursor can beprepared by contacting a solid support with a chromium precursor (achromium source) prior to heat treating. Generally, the chromiumprecursor can comprise CrO₃ or anything calcinable to CrO₃. Typicalchromium precursors, therefore, can include chromium (III) acetate,basic chromium (III) acetate, chromium (III) nitrate, chromium (III)sulfate, chromium (III) chloride (or bromide or iodide), chromium (II)chloride (or bromide or iodide), chromium (III) malate (or propionate,or gluconate, or citrate). These chromium precursors, beneficially, aresoluble in water. Other organic chromium compounds can be used as thechromium precursor, and these can be used with an alcohol or otherorganic solvent, including chromium (III) naphthenate, chromium (III)acetylacetonate and other diketonates, chromyl chloride, chromium (III)alkoxides (e.g., methoxide or ethoxide), and higher carboxylates such aschromium (III) 2-ethyl hexanoate or chromium (III) propionate. Organicchromium (0) compounds also can be used in a hydrocarbon solvent, suchas diarene chromium (0) compounds like bis-cumene chromium (0),bis-benzene chromium (0), bis-toluene chromium (0), and so forth.Similarly, bis-cyclopentadienyl chromium (II), bis-indenyl chromium(II), and other cyclopentadienyl derivatives can be used as the chromiumprecursor, as well as chromium (0) hexacarbonyl. Further, sodium,potassium, or ammonium chromate or dichromate can likewise be used asthe chromium source.

Thus, when the process comprises step (a)(i), the supported chromiumprecursor can comprise CrO₃ (or anything calcinable to CrO₃), chromium(III) acetate, basic chromium (III) acetate, chromium (III) nitrate,chromium (III) sulfate, chromium (III) chloride (or bromide or iodide),chromium (II) chloride (or bromide or iodide), chromium (III) malate (orpropionate, gluconate, or citrate), chromium (III) naphthenate, chromium(III) acetylacetonate (or other diketonate), chromyl chloride, chromium(III) methoxide (or ethoxide or other alkoxide), chromium (III) 2-ethylhexanoate (or propionate or other carboxylate), a chromium (0) compound(e.g., chromium (0) hexacarbonyl, or a diarene chromium (0) compoundsuch as bis-cumene chromium (0), bis-benzene chromium (0), orbis-toluene chromium (0)), a chromium (II) cyclopentadienyl-typecompound (e.g., bis-cyclopentadienyl chromium (II) or bis-indenylchromium (II)), a chromate compound (e.g., potassium chromate, sodiumchromate, ammonium chromate, potassium dichromate, sodium dichromate, orammonium dichromate), and the like, as well as any combination thereof.In a particular aspect, the supported chromium precursor can comprisepotassium chromate, sodium chromate, ammonium chromate, potassiumdichromate, sodium dichromate, ammonium dichromate, or any combinationthereof.

In step (a)(ii), the chromium precursor can be contacted with a solidsupport while heat treating at a peak temperature from about 50° C. toabout 1000° C. to form the supported chromium catalyst comprisingchromium in a hexavalent oxidation state. Certain chromium precursorsare volatile and can be added during the heat treatment. For example,chromium (III) acetylacetonate sublimes above about 100° C., so it canbe dry-mixed with the solid support and the mixture heat treated. Thechromium vaporizes during the heating step and reacts with the supportto form chromium (VI). Chromium (0) hexacarbonyl is another example ofthis approach. Alternatively, chromyl chloride is a liquid thatevaporates easily. Thus, in one aspect, chromyl chloride can bevaporized into a gas stream used to fluidize the solid support duringheat treatment. It passes up through the solid support bed as a vapor,and is adsorbed onto and/or reacts with the solid support. It was foundthat chromium (VI) on these catalysts tends to be mobile on the support,passing easily from one particle to another during heat treatment, andtherefore in another aspect, the support can be dry-mixed with anon-volatile chromium precursor, such as chromic oxide (Cr₂O₃) followedby the heat treatment. The Cr₂O₃ particles are oxidized on the surfaceto chromium (VI) which then contact the support, and pass over onto thesupport. Many other chromium precursors can be used in this way, such asfor example, CrO₃, chromium (III) sulfate, chromium (III) nitrate, andthe like. Other examples include sodium, potassium, or ammonium chromateor dichromate, which is unexpected, because such alkali metal chromatesare not usually acceptable for use in polymerization catalysts becauseof low activity and sintering of the solid support.

Thus, when the process comprises step (a)(ii), the chromium precursorcan comprise chromium (III) acetylacetonate, chromium (0), chromylchloride, chromic oxide (Cr₂O₃), CrO₃, chromium (III) sulfate, chromium(III) nitrate, a chromate compound (e.g., potassium chromate, sodiumchromate, ammonium chromate, potassium dichromate, sodium dichromate, orammonium dichromate), and the like, as well as any combination thereof.In a particular aspect, the chromium precursor can comprise potassiumchromate, sodium chromate, ammonium chromate, potassium dichromate,sodium dichromate, ammonium dichromate, or any combination thereof.

In step (a)(iii), a solid support can be heat treated at a peaktemperature from about 50° C. to about 1000° C. and then contacted witha chromium precursor to form the supported chromium catalyst comprisingchromium in a hexavalent oxidation state. Chromium (VI) can be addedafter the heat treatment. For example, after the solid support is heattreated, it can be impregnated with an anhydrous, non-protic chromium(VI) solution, followed by evaporation of the solvent. It is typicallyimportant for the solvent be non-protic, so as to not re-hydrate thesupport. Examples of this approach include dissolving CrO₃ inacetonitrile and impregnating the heat-treated support with thissolution, followed by evaporation of the solvent. Organic chromium (VI)esters also can be dissolved in hydrocarbons and impregnated onto theheat-treated support. Examples include bis(t-butyl) chromate dissolvedin hexane, or bis(triphenylsilyl)chromate dissolved in toluene. Chromylchloride is another precursor that can be dissolved in hydrocarbonsolvents or acetonitrile, or even used through vapor phase contact withthe support after the heat-treatment. Sodium, potassium, or ammoniumchromate or dichromate can be dissolved in acetonitrile, or even in ahydrocarbon (e.g., a crown-ether may be used to improve the solubility)and utilized as the chromium precursor.

Thus, when the process comprises step (a)(iii), the chromium precursorcan comprise CrO₃, bis(t-butyl) chromate (or bis(triphenylsilyl)chromate, or other organic chromium (VI) ester), chromyl chloride, aninorganic chromate compound (e.g., potassium chromate, sodium chromate,ammonium chromate, potassium dichromate, sodium dichromate, or ammoniumdichromate), and the like, as well as any combination thereof. Thesolvent can be removed, in whole or in part, prior to the irradiatingstep. Alternatively, if the solvent is the desired hydrocarbon reactant,it is not necessary to remove prior to irradiating the hydrocarbonreactant and the supported chromium catalyst.

Step (a) can be conducted at a variety of temperature and timeconditions, as would be recognized by a skilled artisan, and can begenerally selected to convert all or a portion of the chromium tohexavalent chromium. Depending upon whether step (a)(i) or (a)(ii) or(a)(iii) is used and the particular chromium precursor (e.g., a chromium(III) precursor or a chromate/dichromate compound), the peak temperaturein step (a)(i) and (a)(ii) and (a)(iii) can encompass a broad range.Representative ranges for the peak temperature include from about 300°C. to about 1000° C., from about 400° C. to about 870° C., from about300° C. to about 600° C., from about 100° C. to about 500° C., fromabout 50° C. to about 400° C., from about 100° C. to about 300° C., fromabout 50° C. to about 200° C., and the like. These temperature rangesalso are meant to encompass circumstances where the heat treatment isperformed at a series of different temperatures, instead of at a singlefixed temperature, falling within the respective temperature ranges,wherein at least one temperature is within the recited ranges.

Depending upon the temperature, the heat treatment step can function aspredominately a drying step (e.g., 50-300° C.) or predominantly acalcining step (e.g., 500-850° C.). In an aspect, a chromium precursoror a supported chromium precursor in a low oxidation state typicallywill necessitate a higher temperature and oxidizing atmosphere toconvert the chromium into hexavalent chromium. In contrast, in anotheraspect, a chromium precursor or a supported chromium precursor that isalready in the hexavalent state (e.g., chromate or dichromate) may onlyneed a low heat treatment temperature to dry or remove excesswater/moisture prior to exposing the supported chromium catalyst tolight irradiation. Consequently, in this latter aspect, an oxidizingatmosphere may not be necessary.

Likewise, depending upon some of these same factors, step (a)(i) and(a)(ii) and (a)(iii) can be conducted in an oxidizing atmosphere in someaspects, while step (a)(i) and (a)(ii) and (a)(iii) can be conducted inan inert atmosphere in other aspects.

A variety of hydrocarbon reactants can be used in the process to form analcohol compound and/or a carbonyl compound, inclusive of saturatedaliphatic hydrocarbon compounds, unsaturated aliphatic hydrocarboncompounds, linear aliphatic hydrocarbon compounds, branched aliphatichydrocarbon compounds, and cyclic aliphatic hydrocarbon compounds, aswell as combinations thereof. Thus, the hydrocarbon reactant cancomprise a linear alkane compound, a branched alkane compound, a cyclicalkane compound, or a combination thereof. Additionally oralternatively, the hydrocarbon reactant can comprise an aromaticcompound, such as benzene, toluene, and the like, as well as substitutedversions thereof, and including combinations thereof.

Any suitable carbon number hydrocarbon can be used, such that thehydrocarbon reactant can comprise a C_(n) hydrocarbon compound (and thealcohol compound often can comprise a C_(n) alcohol compound, and thecarbonyl compound often can comprise a C_(n) carbonyl compound). Whilenot being limited thereto, the integer n can range from 1 to 36 in oneaspect, from 1 to 18 in another aspect, from 1 to 12 in yet anotheraspect, and from 1 to 8 in still another aspect.

Therefore, the hydrocarbon reactant can comprise any suitable carbonnumber alkane compound, for instance, a C₁ to C₃₆ alkane compound;alternatively, a C₁ to C₁₈ alkane compound; alternatively, a C₁ to C₁₂alkane compound; or alternatively, a C₁ to C₈ alkane compound. Ifdesired, the hydrocarbon reactant can contain a single alkane compoundof relatively high purity, such as at least about 90 wt. % of a singlealkane compound, at least about 95 wt. % of a single alkane compound, atleast about 98 wt. % of a single alkane compound, or at least about 99wt. % of a single alkane compound, and so forth. Alternatively, thehydrocarbon reactant can comprise a mixture of two or more hydrocarbonreactants, such as two or more alkane compounds in any relativeproportions. Thus, the hydrocarbon reactant can comprise a mixture of C₁to C₁₈ alkane compounds, a mixture of C₁ to C₄ alkane compounds, amixture of C₂ to C₆ alkane compounds, a mixture of C₆ to C₈ alkanecompounds, or a mixture of C₁₀ to C₁₄ alkane compounds, and the like.

Similarly, the hydrocarbon reactant can comprise any suitable carbonnumber olefin compound, for instance, a C₂ to C₃₆ olefin compound;alternatively, a C₂ to C₁₈ olefin compound; alternatively, a C₂ to C₁₂olefin compound; or alternatively, a C₂ to C₈ olefin compound. As above,if desired, the hydrocarbon reactant can contain a single olefincompound of relatively high purity, such as at least about 90 wt. % of asingle olefin compound, at least about 95 wt. % of a single olefincompound, at least about 98 wt. % of a single olefin compound, or atleast about 99 wt. % of a single olefin compound, and so forth.Alternatively, the hydrocarbon reactant can comprise a mixture of two ormore hydrocarbon reactants, such as two or more olefin compounds in anyrelative proportions. Thus, the hydrocarbon reactant can comprise amixture of C₂ to C₃₆ olefin compounds, a mixture of C₂ to C₁₈ olefincompounds, a mixture of C₂ to C₁₂ olefin compounds, or a mixture of C₂to C₈ olefin compounds, and the like.

Likewise, the hydrocarbon reactant can comprise any suitable carbonnumber aromatic compound, for instance, a C₆ to C₃₆ aromatic compound;alternatively, a C₆ to C₁₈ aromatic compound; alternatively, a C₆ to C₁₂aromatic compound; or alternatively, a C₆ to C₈ aromatic compound. Asabove, if desired, the hydrocarbon reactant can contain a singlearomatic compound of relatively high purity, such as at least about 90wt. % of a single aromatic compound, at least about 95 wt. % of a singlearomatic compound, at least about 98 wt. % of a single aromaticcompound, or at least about 99 wt. % of a single aromatic compound, andso forth. Alternatively, the hydrocarbon reactant can comprise a mixtureof two or more hydrocarbon reactants, such as two or more aromaticcompounds in any relative proportions. Thus, the hydrocarbon reactantcan comprise a mixture of C₆ to C₃₆ aromatic compounds, a mixture of C₆to C₁₈ aromatic compounds, a mixture of C₆ to C₁₂ aromatic compounds, ora mixture of C₆ to C₈ aromatic compounds, and the like.

Illustrative examples of alkane, olefin, and aromatic hydrocarbonreactants can include methane, ethane, propane, butane (e.g., n-butaneor isobutane), pentane (e.g., n-pentane, neopentane, or isopentane),hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane,tetradecane, pentadecane, hexadecane, heptadecane, octadecane, ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene,cyclohexene, benzene, toluene, ethylbenzene, xylene, mesitylene, and thelike, as well as combinations thereof.

Thus, the hydrocarbon reactant can comprise a mixture of an aliphatichydrocarbon and an aromatic hydrocarbon. In a non-limiting aspect, thehydrocarbon reactant can comprise methane; alternatively, ethane;alternatively, propane; alternatively, butane; alternatively, pentane;alternatively, hexane; alternatively, heptane; alternatively, octane;alternatively, nonane; alternatively, decane; alternatively, undecane;alternatively, dodecane; alternatively, tridecane; alternatively,tetradecane; alternatively, pentadecane; alternatively, hexadecane;alternatively, heptadecane; alternatively, octadecane; alternatively,ethylene; alternatively, propylene; alternatively, 1-butene;alternatively, 1-pentene; alternatively, 1-hexene; alternatively,1-heptene; alternatively, 1-octene; alternatively, 1-decene;alternatively, 1-dodecene; alternatively, 1-tetradecene; alternatively,1-hexadecene; alternatively, 1-octadecene; alternatively, cyclopentene;alternatively, cyclohexene; alternatively, benzene; alternatively,toluene; alternatively, ethylbenzene; alternatively, xylene; oralternatively, mesitylene.

In an aspect, the hydrocarbon (alkane) reactant can comprise methane,ethane, propane, n-butane, isobutane, n-pentane, neopentane, isopentane,n-hexane, n-heptane, n-octane, n-decane, n-dodecane, and the like, orany combination thereof, while in another aspect, the hydrocarbon(alkane) reactant can comprise methane, ethane, propane, butane,pentane, hexane, and the like, or any combination thereof. In yetanother aspect, the hydrocarbon (olefin) reactant can comprise ethylene,propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-decene,1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, cyclopentene,cyclohexene, and the like, or any combination thereof, or alternatively,ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene,or any combination thereof. In still another aspect, the hydrocarbon(aromatic) reactant can comprise benzene, toluene, ethylbenzene, xylene,mesitylene, and the like, or any combination thereof.

Generally, the irradiating step can be performed under any conditionssufficient to accommodate the irradiation of the hydrocarbon reactantand the supported chromium catalyst (comprising chromium in a hexavalentoxidation state) with a light beam and to form the reduced chromiumcatalyst (having a lower oxidation state). The irradiation step cancomprise reducing at least a portion of the hexavalent chromium speciesto a reduced oxidation state—for instance, Cr (II) and/or Cr (III)and/or Cr (IV) and/or Cr (V) species, any of which may be present on thereduced chromium catalyst.

The relative amount (or concentration) of the hydrocarbon reactant tothe amount of chromium (in the supported chromium catalyst) can alterthe efficacy of the reduction process. In certain aspects, the molarratio of the hydrocarbon reactant to the chromium (in the supportedchromium catalyst) can be at least about 0.25:1, at least about 0.5:1,at least about 1:1, at least about 10:1, at least about 100:1, at leastabout 1000:1, or at least about 10,000:1. Thus, a large excess of thehydrocarbon reactant can be used, and there is no particular limit as tothe maximum amount of hydrocarbon reactant.

The temperature and pressure of the irradiating step can be such thatthe hydrocarbon reactant remains a liquid throughout reduction of thesupported chromium catalyst in one aspect, and the hydrocarbon remains agas throughout reduction of the supported chromium catalyst in anotheraspect. Advantageously, it was found that reducing supported chromiumcompounds at lower temperatures than those typically required to reducehexavalent chromium species using heat and not light, was possible bythe irradiating steps disclosed herein. In certain aspects, theirradiating step can be conducted at a temperature of less than about200° C., less than about 100° C., less than about 70° C., less thanabout 40° C., from about 0° C. to about 200° C., from about −100° C. toabout 100° C., from about 0° C. to about 100° C., or from about 10° C.to about 40° C., and can produce a reduced chromium catalyst (e.g., withat least a portion of the chromium on the reduced chromium catalysthaving at least one bonding site with a hydrocarboxy group). Thesetemperature ranges also are meant to encompass circumstances where theirradiation is performed at a series of different temperatures, insteadof at a single fixed temperature, falling within the respectivetemperature ranges, wherein at least one temperature is within therecited ranges.

The irradiating step can be further characterized by an amount of timethat the hydrocarbon reactant and supported chromium catalyst areexposed to the light beam, e.g., an exposure time. Without being boundby theory, it is believed that exposure to the light beam in thepresence of the hydrocarbon reactant is responsible for the reduction ofthe supported chromium catalyst, and therefore it follows that theexposure time must be sufficient to allow this transformation to occur,whether the transformation occurs very rapidly or very slowly. Thus, incertain aspects, and not being limited thereto, the exposure time can bein a range from about 15 sec to about 48 hr, from about 15 sec to about24 hr, from about 1 hr to about 8 hr, from about 15 min to about 4 hr,from about 1 min to about 6 hr, from about 5 min to about 1 hr, fromabout 10 min to about 2 hr, from about 1 min to about 1 hr, or fromabout 1 min to about 15 min. As one of skill in the art would recognize,the exposure time can vary based on the intensity of the light beam, thewavelength(s) of the light beam, and so forth. Agitation, mixing, orother suitable technique can be used to ensure that the mixture of thesupported chromium catalyst (e.g., particles) and the hydrocarbonreactant is uniformly exposed to the light beam irradiation.

The supported chromium catalyst and the hydrocarbon reactant can becontinuously subjected to irradiation (for the entirety of the exposuretime), or the irradiation can be pulsed (such that the total of thepulses equates to the exposure time, e.g., sixty 1-sec pulses equates toa 60-sec exposure time). Combinations of periods of continuousirradiation and pulsed irradiation can be utilized, if desired.

In the disclosed processes, irradiation of a supported chromium catalystwith a light beam in the UV-visible spectrum, in the presence of ahydrocarbon reactant, results in a chromium catalyst with a reducedoxidation state (e.g., a reduced chromium catalyst). A wide range ofwavelengths, light sources, and intensities can be used, as long asthese wavelengths, light sources, and intensities are sufficient toreduce at least a portion of the hexavalent chromium species present inthe supported chromium catalyst. In certain aspects, for instance, thelight can be derived from any suitable source, such as from sunlight, afluorescent white light, an LED diode, and/or a UV lamp. The distancefrom non-sunlight sources can be varied as needed (e.g., minimized) toincrease the effectiveness of the irradiation.

The wavelength of the light can be any in the range of UV-visible light.In certain aspects, the wavelength of the light beam can be a singlewavelength, or more than one wavelength, such as a range of wavelengths.For instance, the wavelength of the light beam can be a range ofwavelengths spanning at least 25 nm, at least 50 nm, at least 100 nm, atleast 200 nm, or at least 300 nm. In one aspect, the wavelength of thelight beam can comprise a single wavelength or a range of wavelengths inthe UV spectrum, in the visible spectrum (from 380 nm to 780 nm), orboth. In another aspect, the wavelength of the light beam can comprise asingle wavelength or a range of wavelengths in the 200 nm to 750 nmrange. Yet, in another aspect, the wavelength of the light beam cancomprise a single wavelength or a range of wavelengths in the 300 to 750nm range, the 350 nm to 650 nm range, the 300 nm to 600 nm range, the300 nm to 500 nm range, or the 400 nm to 500 nm range. In other aspects,the wavelength of the light beam can comprise a single wavelength or arange of wavelengths below 600 nm, below 525 nm, or below 500 nm;additionally or alternatively, above 300 nm, above 350 nm, above 400 nm,or above 450 nm.

The light beam of the irradiating step also can be characterized by itsintensity (e.g., the total amount of light emitted from a source). Incertain aspects, the light beam can have an intensity of at least about500 lumens, at least about 1,000 lumens, at least about 2,000 lumens atleast about 5,000 lumens, at least about 10,000 lumens, at least about20,000 lumens, at least about 50,000 lumens, or at least about 100,000lumens. Thus, there may not be an upper limit on the intensity of thelight source. Alternatively, the light beam can have an intensity in arange from about 50 to about 50,000 lumens, from about 50 to about10,000 lumens, from about 100 to about 5,000 lumens, or from about 500to about 2,000 lumens. Additionally, the light beam can be characterizedby the amount of light reaching the hydrocarbon reactant and supportedchromium catalyst, i.e., the flux. In certain aspects, the hydrocarbonreactant and the supported chromium catalyst comprising chromium in ahexavalent oxidation state can be irradiated by at least about 100 lux,at least about 500 lux, at least about 1000 lux, at least about 2000lux, at least about 5000 lux, at least about 10,000 lux, at least about20,000 lux, at least about 100,000 lux, or in a range from about 10,000to about 1,000,000 lux, from about 50,000 to about 500,000 lux, or fromabout 50,000 to about 200,000 lux. Additionally or alternatively, incertain aspects, the hydrocarbon reactant and the supported chromiumcatalyst comprising chromium in the hexavalent oxidation state can beirradiated with a light beam having a power of at least about 50 watts,at least about 100 watts, at least about 200 watts, at least about 500watts, at least about 1,000 watts, or at least about 2,000 watts.

Any suitable reactor or vessel can be used to form the alcohol compoundand/or the carbonyl compound, non-limiting examples of which can includea flow reactor, a continuous reactor, a packed bed reactor, a fluidizedbed reactor, and a stirred tank reactor, including more than one reactorin series or in parallel, and including any combination of reactor typesand arrangements.

In one aspect, the hydrocarbon reactant can be in a gas phase during theirradiating step. In another aspect, the hydrocarbon reactant can be ina liquid phase during the irradiating step. In another aspect, thedisclosed processes can comprise irradiating a slurry (e.g., a loopslurry) of the solid supported chromium catalyst in the hydrocarbonreactant. In yet another aspect, the disclosed processes can comprisecontacting the hydrocarbon reactant with a fluidized bed of the solidsupported chromium catalyst, and irradiating while contacting(fluidizing). In still another aspect, the disclosed processes cancomprise contacting the hydrocarbon reactant (e.g., in the gas phase orin the liquid phase) with a fixed bed of the solid supported chromiumcatalyst, and irradiating while contacting. As a skilled artisan wouldrecognize, there are other methods for contacting the hydrocarbonreactant and the solid supported chromium catalysts and irradiating, andthe disclosed processes are not limited solely to those disclosedherein. For instance, the hydrocarbon reactant and the supportedchromium catalyst can be mixed or contacted in a stirred tank, andirradiated while being mixed in the stirred tank.

Any suitable pressure can be used to contact the hydrocarbon reactantand the supported catalyst and to form the reduced chromium catalyst,and such can depend upon the carbon number of the hydrocarbon reactant(and its boiling point), the type of reactor configuration and desiredmode for contacting the hydrocarbon reactant with the (solid) supportedchromium catalyst, among other considerations.

Often, the process for forming the reduced chromium catalyst (andsubsequently, the alcohol and/or carbonyl compound) can be a flowprocess and/or a continuous process. In such circumstances, thehydrocarbon reactant-supported chromium catalyst contact time (orreaction time) can be expressed in terms of weight hourly space velocity(WHSV)—the ratio of the weight of the hydrocarbon reactant which comesin contact with a given weight of the supported chromium catalyst perunit time (units of g/g/hr, or hr⁻¹).

While not limited thereto, the WHSV employed for the disclosed processescan have a minimum value of 0.01 hr⁻¹, 0.02 hr⁻¹, 0.05 hr⁻¹, 0.1 hr⁻¹,0.25 hr⁻¹, or 0.5 hr⁻¹; or alternatively, a maximum value of 500 hr⁻¹,400 hr⁻¹, 300 hr⁻¹, 100 hr⁻¹, 50 hr⁻¹, 10 hr⁻¹, 5 hr⁻¹, 2 hr⁻¹, or 1hr⁻¹. Generally, the WHSV can be in a range from any minimum WHSVdisclosed herein to any maximum WHSV disclosed herein. In a non-limitingaspect, the WHSV can be in a range from about 0.01 hr⁻¹ to about 500hr⁻¹; alternatively, from about 0.01 h⁻¹ to about 10 hr⁻¹;alternatively, from about 0.01 hr⁻¹ to about 1 hr⁻¹; alternatively, fromabout 0.02 hr⁻¹ to about 400 hr⁻¹; alternatively, from about 0.02 hr⁻¹to about 50 hr⁻¹; alternatively, from about 0.05 hr⁻¹ to about 300 hr⁻¹;alternatively, from about 0.05 hr⁻¹ to about 5 hr⁻¹; alternatively, fromabout 0.1 hr⁻¹ to about 400 hr⁻¹; alternatively, from about 0.25 hr⁻¹ toabout 50 hr⁻¹; alternatively, from about 0.25 hr⁻¹ to about 2 hr⁻¹;alternatively, from about 0.5 hr⁻¹ to about 400 hr⁻¹; alternatively,from about 0.5 hr⁻¹ to about 5 hr⁻¹; or alternatively, from about 0.5hr⁻¹ to about 2 hr⁻¹. Other WHSV ranges are readily apparent from thisdisclosure.

Referring now to the hydrolyzing step, in which the reduced chromiumcatalyst (e.g., with at least a portion of the chromium on the reducedchromium catalyst having at least one bonding site with a hydrocarboxygroup) is hydrolyzed to form a reaction product comprising the alcoholcompound and/or the carbonyl compound. Generally, the temperature,pressure, and time features of the hydrolyzing step can be the same asthose disclosed herein for the irradiating step, although not limitedthereto. For example, the hydrolyzing step can be conducted at atemperature of less than about 200° C., less than about 100° C., lessthan about 70° C., less than about 40° C., from about 0° C. to about200° C., from about 0° C. to about 100° C., or from about 10° C. toabout 40° C., and can result in the formation of a reaction productcontaining the alcohol compound and/or the carbonyl compound. Thesetemperature ranges also are meant to encompass circumstances where thehydrolyzing step is performed at a series of different temperatures,instead of at a single fixed temperature, falling within the respectivetemperature ranges, wherein at least one temperature is within therecited ranges.

While not limited thereto, the hydrolyzing step can comprise contactingthe reduced chromium catalyst with a hydrolysis agent. Illustrative andnon-limiting examples of suitable hydrolysis agents can include water,steam, an alcohol agent, an acid agent, an alkaline agent, and the like,as well as combinations thereof. Thus, mixtures of water and variousalcohol agents, such as C₁-C₄ alcohols (and/or acid agents, such ashydrochloric acid, sulfuric acid, acetic acid, ascorbic acid, and thelike; and/or alkaline agents, such as sodium hydroxide, ammoniumhydroxide, and the like) in any relative proportions can be used as thehydrolysis agent. Thus, the pH of the hydrolysis agent(s) can range fromacid to neutral to basic pH values, generally encompassing a pH rangefrom about 1 (or less) to about 13-13.5.

Optionally, the hydrolysis agent can further comprise any suitablereducing agent, and representative reducing agents include ascorbicacid, iron (II) reducing agents, zinc reducing agents, and the like, aswell as combinations thereof. These are sometimes useful for preventingunwanted secondary oxidations by unreacted chromium (VI). Further, theyalso can be used to tailor the product range by increasing selectivity.For example, in some aspects, adding reducing agents to the hydrolysisagent can eliminate all carbonyl products and instead produce onlyalcohol products.

As disclosed herein, the reaction product can comprise an alcoholcompound and/or a carbonyl compound, which can be an analog of thehydrocarbon reactant. Thus, typical alcohol compounds that can besynthesized using the processes disclosed herein can include, forinstance, methanol, ethanol, isopropanol, butanols, pentanols, hexanols,heptanols, octanols, nonanols, decanols, undecanols, dodecanols,tridecanols, tetradecanols, pentadecanols, hexadecanols, heptadecanols,octadecanols, benzyl alcohol, phenols, xylenols, and the like, as wellas combinations thereof. Herein, an alcohol compound encompassesmono-alcohol compounds as well as diol compounds (e.g., ethanediol andhexanediols).

In addition to or in lieu of the alcohol compound, the reaction productcan comprise a carbonyl compound, such as an aldehyde compound, a ketonecompound, or an organic acid compound, as well as any combination ofaldehyde, ketone, and organic acid compounds. Thus, enols areencompassed herein, since the reaction product can comprise an alcoholcompound, a carbonyl compound, or both. In some aspects, the alcohol orcarbonyl product can contain unsaturation. For example, the carbon(s)adjacent to the alcohol or carbonyl group can contain a double bond.While not wishing to be bound by theory, it is believed that the allylC—H bond is particularly susceptible to being attacked by the chromium(VI). Thus, when the reductant hydrocarbon has a double bond, a typicalalcohol product, and often among the most abundant, contains the —OHgroup on the adjacent allyl carbon.

The processes described herein result in an unexpectedly high conversionof the hydrocarbon reactant and/or yield to the alcohol compound (orcarbonyl compound). In one aspect, the minimum conversion (or yield) canbe at least about 2 wt. %, at least about 5 wt. %, at least about 10 wt.%, at least about 15 wt. %, or at least about 25 wt. %. Additionally,the maximum conversion (or yield) can be about 50 wt. %, about 70 wt. %,about 80 wt. %, about 90 wt. %, about 95 wt. %, or about 99 wt. %, andcan approach 100% conversion of the hydrocarbon reactant (or yield ofthe alcohol compound, or yield of the carbonyl compound). Generally, theconversion (or yield) can be in a range from any minimum conversion (oryield) disclosed herein to any maximum conversion (or yield) disclosedherein. Non-limiting ranges of conversion (or yield) can include fromabout 5 wt. % to about 99 wt. %, from about 10 wt. % to about 95 wt. %,or from about 15 wt. % to about 70 wt. %. For conversion, thepercentages are the amount of the hydrocarbon reactant converted basedon the initial amount of the hydrocarbon reactant. The yield values areweight percentages, and are based on the weight of the alcohol compound(or carbonyl compound) produced to the weight of hydrocarbon reactant.In some aspects, these conversions (or yields) can be achieved in abatch process, while in other aspects, these conversions (or yields) canbe achieved in a flow or continuous process, such as, for example, asingle pass or multiple passes through a reactor (e.g., a fixed bedreactor). Often, the conversion and yield can be manipulated by varyingthe ratio of reductant hydrocarbon feed to the amount of chromium (VI),and by varying other reaction conditions such as time, temperature, andirradiation.

Also unexpectedly, continuous flow processes for producing the alcoholcompound and/or carbonyl compound in accordance with this invention haveunexpectedly high single pass conversions of the hydrocarbon reactant(or single pass yields to the desired alcohol or carbonyl compound). Inone aspect, the minimum single pass conversion (or yield) can be atleast about 2 wt. %, at least about 5 wt. %, at least about 10 wt. %, atleast about 15 wt. %, or at least about 25 wt. %. Additionally, themaximum single pass conversion (or yield) can be about 50 wt. %, about70 wt. %, about 80 wt. %, about 90 wt. %, about 95 wt. %, or about 99wt. %, and can approach 100% conversion of the hydrocarbon reactant (oryield of the alcohol compound, or yield of the carbonyl compound),depending upon the reaction conditions. Generally, the single passconversion (or yield) can be in a range from any minimum single passconversion (or yield) disclosed herein to any maximum single passconversion (or yield) disclosed herein. Non-limiting ranges of singlepass conversion (or yield) can include from about 5 wt. % to about 99wt. %, from about 10 wt. % to about 95 wt. %, or from about 15 wt. % toabout 70 wt. %.

The yield of the alcohol compound (or carbonyl compound) also can becharacterized based on the amount of chromium (VI) (of the supportedchromium catalyst). For instance, the molar ratio (molar yield) of thealcohol compound (or carbonyl compound) based on the moles of chromium(VI) can be at least about 0.01 moles, at least about 0.02 moles, atleast about 0.05 moles, at least about 0.1 moles, or at least about 0.25moles (and up to 2 moles, up to about 1.8 moles, up to about 1.6 moles,up to about 1.4 moles, up to about 1.2 moles, or up to about 1 mole) ofthe alcohol compound (or carbonyl compound) per mole of chromium (VI).If more than one alcohol compound and/or carbonyl compound is/areproduced, then this ratio represents the total moles of alcohol and/orcarbonyl compounds produced per mole of chromium (VI).

The processes to produce the alcohol compounds and/or carbonyl compoundsdisclosed herein typically can result in—after hydrolysis—a crudereaction mixture containing residual hydrocarbon reactant (e.g.,methane), a desired alcohol compound and/or carbonyl compound (e.g.,methanol), and by-products. In many instances, it can be desirable toisolate or separate at least a portion (and in some cases, all) of thehydrocarbon reactant from the reaction product after step (c). This canbe accomplished using any suitable technique, which can include but isnot limited to, extraction, filtration, evaporation, or distillation, aswell as combinations of two or more of these techniques. In particularaspects of this invention, the isolating or separating step utilizesdistillation at any suitable pressure (one or more than one distillationcolumn can be used).

Additionally or alternatively, the processes disclosed herein canfurther comprise a step of separating at least a portion (and in somecases, all) of the alcohol compound (or carbonyl compound) from thereaction product, and any suitable technique can be used, such asextraction, filtration, evaporation, distillation, or any combinationthereof. Additionally or alternatively, the processes disclosed hereincan further comprise a step of separating at least a portion (and insome cases, all) of the reduced chromium catalyst from the reactionproduct after step (c), and as above, any suitable technique(s) can beused.

Optionally, certain components of the reaction product—such as thehydrocarbon reactant—can be recovered and recycled to the reactor. Insuch instances, at least a portion (and in some cases, all) of thehydrocarbon reactant can be recycled and contacted with supportedchromium catalyst again, such that the overall conversion of thehydrocarbon product is increased after multiple contacts with thesupported chromium catalyst (or multiple passes through the reactorcontaining the supported chromium catalyst).

If desired, the processes disclosed herein can further comprise a stepof (d) calcining at least a portion (and in some cases, all) of thereduced chromium catalyst to regenerate the supported chromium catalyst.Any suitable calcining conditions can be used, for instance, subjectingthe reduced chromium catalyst to an oxidizing atmosphere at any suitablecalcining temperature and time conditions, such as a calciningtemperature from about 300° C. to about 1000° C., from about 500° C. toabout 900° C., or from about 550° C. to about 870° C., for a time periodof from about 1 min to about 24 hr, from about 1 hr to about 12 hr, orfrom about 30 min to about 8 hr.

The calcining step can be conducted using any suitable technique andequipment, whether batch or continuous. For instance, the calcining stepcan be performed in a belt calciner or, alternatively, a rotarycalciner. In some aspects, the calcining step can be performed in abatch or continuous calcination vessel comprising a fluidized bed. Aswould be recognized by those of skill in the art, other suitabletechniques and equipment can be employed for the calcining step, andsuch techniques and equipment are encompassed herein.

An illustrative and non-limiting example of the processes disclosedherein follows for the case in which a C₁-C₆ alkane is the hydrocarbonreactant, and a C₁-C₆ alcohol is the alcohol product. In this case, theprocess for converting a C₁-C₆ alkane into a C₁-C₆ alcohol can comprise(a)(i) heat treating a supported chromium precursor at a peaktemperature from about 50° C. to about 1000° C. to form a supportedchromium catalyst comprising chromium in a hexavalent oxidation state,or (a)(ii) contacting a chromium precursor with a solid support whileheat treating at a peak temperature from about 50° C. to about 1000° C.to form a supported chromium catalyst comprising chromium in ahexavalent oxidation state, or (a)(iii) heat treating a solid support ata peak temperature from about 50° C. to about 1000° C. and thencontacting a chromium precursor with the solid support to form asupported chromium catalyst comprising chromium in a hexavalentoxidation state, (b) irradiating the C₁-C₆ alkane and the supportedchromium catalyst with a light beam at a wavelength in the UV-visiblespectrum to reduce at least a portion of the supported chromium catalystto form a reduced chromium catalyst, and (c) hydrolyzing the reducedchromium catalyst (with any suitable hydrolysis agent) to form areaction product comprising the C₁-C₆ alcohol.

The C₁-C₆ alkane can comprise methane (or ethane, or propane, or butane,or pentane, or hexane) and the C₁-C₆ alcohol can comprise methanol (orethanol, or propanol, or butanol, or pentanol, or hexanol). The reactionproduct can, in some aspects, further comprise an organic acid compound.For instance, when the reactant comprises methane, the reaction productcan comprise methanol, and in some aspects, can further comprise formicacid. Moreover, as discussed herein, the process to convert a C₁-C₆alkane into a C₁-C₆ alcohol optionally can further comprise a step of(d) calcining at least a portion (and in some cases, all) of the reducedchromium catalyst to regenerate the supported chromium catalyst.

The C₁-C₆ alkane can comprise methane (or ethane, or propane, or butane,or pentane, or hexane, or cyclopentane, or cyclohexane) and the C₁-C₆alcohol can comprise methanol (or ethanol, or propanols, or butanols, orpentanols, or hexanols, or cyclopentanol, or cyclohexanol). The reactionproduct can, in some aspects, further comprise an organic acid compound.For instance, when the reactant comprises methane, the reaction productcan comprise methanol, and in some aspects, can further comprise formicacid. When the reactant is ethane or ethylene, the reaction product cancomprise methanol, ethanol, formic acid and/or acetic acid. Moreover, asdiscussed herein, the process to convert a C₁-C₆ alkane into a C₁-C₆alcohol optionally can further comprise a step of (d) calcining at leasta portion (and in some cases, all) of the reduced chromium catalyst toregenerate the supported chromium catalyst.

Chromium Catalysts

Various solid supports can be used for the supported chromium precursor,the supported chromium catalyst, and the reduced chromium catalyst, suchas conventional solid oxides and zeolites. Generally, the solid oxidecan comprise oxygen and one or more elements selected from Group 2, 3,4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, or 15 of the periodic table, orcomprise oxygen and one or more elements selected from the lanthanide oractinide elements (See: Hawley's Condensed Chemical Dictionary, 11^(th)Ed., John Wiley & Sons, 1995; Cotton, F. A., Wilkinson, G., Murillo, C.A., and Bochmann, M., Advanced Inorganic Chemistry, 6^(th) Ed.,Wiley-Interscience, 1999). For example, the solid oxide can compriseoxygen and an element, or elements, selected from Al, B, Be, Bi, Cd, Co,Cr, Cu, Fe, Ga, La, Mn, Mo, Ni, Sb, Si, Sn, Sr, Th, Ti, V, W, P, Y, Zn,and Zr. Illustrative examples of solid oxide materials or compounds thatcan be used as solid support can include, but are not limited to, Al₂O₃,B₂O₃, BeO, Bi₂O₃, CdO, Co₃O₄, Cr₂O₃, CuO, Fe₂O₃, Ga₂O₃, La₂O₃, Mn₂O₃,MoO₃, NiO, P₂O₅, Sb₂O₅, SiO₂, SnO₂, SrO, ThO₂, TiO₂, V₂O₅, WO₃, Y₂O₃,ZnO, ZrO₂, and the like, including mixed oxides thereof, andcombinations thereof.

The solid oxide can encompass oxide materials such as silica, “mixedoxide” compounds thereof such as silica-titania, and combinations ormixtures of more than one solid oxide material. Mixed oxides such assilica-titania can be single or multiple chemical phases with more thanone metal combined with oxygen to form the solid oxide. Examples ofmixed oxides that can be used as solid oxide include, but are notlimited to, silica-alumina, silica-coated alumina, silica-titania,silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate,alumina-boria, silica-boria, aluminum phosphate, aluminophosphate,aluminophosphate-silica, titania-zirconia, and the like, or acombination thereof. In some aspects, the solid support can comprisesilica, silica-alumina, silica-coated alumina, silica-titania,silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria,aluminophosphate-silica, and the like, or any combination thereof.Silica-coated aluminas are encompassed herein; such oxide materials aredescribed in, for example, U.S. Pat. Nos. 7,884,163 and 9,023,959,incorporated herein by reference in their entirety.

The percentage of each oxide in a mixed oxide can vary depending uponthe respective oxide materials. As an example, a silica-alumina (orsilica-coated alumina) typically has an alumina content from 5 wt. % to95 wt. %. According to one aspect, the alumina content of thesilica-alumina (or silica-coated alumina) can be from 5 wt. % alumina 50wt. % alumina, or from 8 wt. % to 30 wt. % alumina. In another aspect,high alumina content silica-aluminas (or silica-coated aluminas) can beemployed, in which the alumina content of these materials typicallyranges from 60 wt. % alumina to 90 wt. % alumina, or from 65 wt. %alumina to 80 wt. % alumina.

In one aspect, the solid oxide can comprise silica-alumina,silica-coated alumina, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, silica-boria, aluminumphosphate, aluminophosphate, aluminophosphate-silica, titania-zirconia,or a combination thereof alternatively, silica-alumina; alternatively,silica-coated alumina; alternatively, silica-titania; alternatively,silica-zirconia; alternatively, alumina-titania; alternatively,alumina-zirconia; alternatively, zinc-aluminate; alternatively,alumina-boria; alternatively, silica-boria; alternatively, aluminumphosphate; alternatively, aluminophosphate; alternatively,aluminophosphate-silica; or alternatively, titania-zirconia.

In another aspect, the solid oxide can comprise silica, alumina,titania, thoria, stania, zirconia, magnesia, boria, zinc oxide, a mixedoxide thereof, or any mixture thereof. In yet another aspect, the solidsupport can comprise silica, alumina, titania, or a combination thereof;alternatively, silica; alternatively, alumina; alternatively, titania;alternatively, zirconia; alternatively, magnesia; alternatively, boria;or alternatively, zinc oxide. In still another aspect, the solid oxidecan comprise silica, alumina, silica-alumina, silica-coated alumina,aluminum phosphate, aluminophosphate, heteropolytungstate, titania,zirconia, magnesia, boria, zinc oxide, silica-titania, silica-yttria,silica-zirconia, alumina-titania, alumina-zirconia, zinc-aluminate,alumina-boria, silica-boria, aluminophosphate-silica, titania-zirconia,and the like, or any combination thereof.

Consistent with certain aspects of this invention, the supportedchromium precursor, the supported chromium catalyst, and the reducedchromium catalyst can comprise a chemically-treated solid oxide as thesolid support, and where the chemically-treated solid oxide comprises asolid oxide (any solid oxide disclosed herein) treated with anelectron-withdrawing anion (any electron withdrawing anion disclosedherein). The electron-withdrawing component used to treat the solidoxide can be any component that increases the Lewis or Brønsted acidityof the solid oxide upon treatment (as compared to the solid oxide thatis not treated with at least one electron-withdrawing anion). Accordingto one aspect, the electron-withdrawing component can be anelectron-withdrawing anion derived from a salt, an acid, or othercompound, such as a volatile organic compound, that serves as a sourceor precursor for that anion. Examples of electron-withdrawing anions caninclude, but are not limited to, sulfate, bisulfate, fluoride, chloride,bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, tungstate, molybdate, and the like,including mixtures and combinations thereof. In addition, other ionic ornon-ionic compounds that serve as sources for these electron-withdrawinganions also can be employed.

It is contemplated that the electron-withdrawing anion can be, or cancomprise, fluoride, chloride, bromide, phosphate, triflate, bisulfate,or sulfate, and the like, or any combination thereof, in some aspectsprovided herein. In other aspects, the electron-withdrawing anion cancomprise sulfate, bisulfate, fluoride, chloride, bromide, iodide,fluorosulfate, fluoroborate, phosphate, fluorophosphate,trifluoroacetate, triflate, fluorozirconate, fluorotitanate, and thelike, or combinations thereof. Yet, in other aspects, theelectron-withdrawing anion can comprise fluoride and/or sulfate.

The chemically-treated solid oxide generally can contain from about 1wt. % to about 30 wt. % of the electron-withdrawing anion, based on theweight of the chemically-treated solid oxide. In particular aspectsprovided herein, the chemically-treated solid oxide can contain fromabout 1 to about 20 wt. %, from about 2 wt. % to about 20 wt. %, fromabout 3 wt. % to about 20 wt. %, from about 2 wt. % to about 15 wt. %,from about 3 wt. % to about 15 wt. %, from about 3 wt. % to about 12 wt.%, or from about 4 wt. % to about 10 wt. %, of the electron-withdrawinganion, based on the total weight of the chemically-treated solid oxide.

In an aspect, the chemically-treated solid oxide can comprise fluoridedalumina, chlorided alumina, bromided alumina, sulfated alumina,fluorided silica-alumina, chlorided silica-alumina, bromidedsilica-alumina, sulfated silica-alumina, fluorided silica-zirconia,chlorided silica-zirconia, bromided silica-zirconia, sulfatedsilica-zirconia, fluorided silica-titania, fluorided silica-coatedalumina, fluorided-chlorided silica-coated alumina, sulfatedsilica-coated alumina, phosphated silica-coated alumina, and the like,as well as any mixture or combination thereof.

In another aspect, the chemically-treated solid oxide employed in thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst, and the processes describedherein can be, or can comprise, a fluorided solid oxide and/or asulfated solid oxide, non-limiting examples of which can includefluorided alumina, sulfated alumina, fluorided silica-alumina, sulfatedsilica-alumina, fluorided silica-zirconia, fluorided silica-coatedalumina, sulfated silica-coated alumina, and the like, as well ascombinations thereof. Additional information on chemically-treated solidoxide can be found in, for instance, U.S. Pat. Nos. 7,294,599,7,601,665, 7,884,163, 8,309,485, 8,623,973, and 8,703,886, which areincorporated herein by reference in their entirety.

Representative examples of the supported chromium precursors, supportedchromium catalysts, and reduced chromium catalysts (in which a solidoxide is the solid support) include, but are not limited to,chromium/silica, chromium/silica-titania,chromium/silica-titania-magnesia, chromium/silica-alumina,chromium/silica-coated alumina, chromium/aluminophosphate,chromium/alumina, chromium/alumina borate, and the like, or anycombination thereof. In one aspect, for instance, the supported chromiumprecursor, the supported chromium catalyst, and the reduced chromiumcatalyst can comprise chromium/silica, while in another aspect, thesupported chromium precursor, the supported chromium catalyst, and thereduced chromium catalyst can comprise chromium/silica-titania, and inyet another aspect, the supported chromium precursor, the supportedchromium catalyst, and the reduced chromium catalyst can comprisechromium/silica-alumina and/or chromium/silica-coated alumina. Incircumstances in which the supported chromium precursor, the supportedchromium catalyst, and the reduced chromium catalyst comprisechromium/silica-titania, any suitable amount of titanium can be present,including from about 0.1 to about 20 wt. %, from about 0.5 to about 15wt. %, from about 1 to about 10 wt. %, or from about 1 to about 6 wt. %titanium, based on the total weight of the respective supported chromiumprecursor, supported chromium catalyst, and reduced chromium catalyst.

Representative examples of supported chromium precursors, supportedchromium catalysts, and reduced chromium catalysts (in which achemically-treated solid oxide is the solid support) include, but arenot limited to, chromium/sulfated alumina, chromium/fluorided alumina,chromium/fluorided silica-alumina, chromium/fluorided silica-coatedalumina, and the like, as well as combinations thereof.

Consistent with certain aspects of this invention, the supportedchromium precursor, the supported chromium catalyst, and the reducedchromium catalyst can comprise a zeolite as the solid support, i.e., achromium supported zeolite. Any suitable zeolite can be used, forinstance, large pore and medium pore zeolites. Large pore zeolites oftenhave average pore diameters in a range of from about 7 Å to about 12 Å,and non-limiting examples of large pore zeolites include L-zeolite,Y-zeolite, mordenite, omega zeolite, beta zeolite, and the like. Mediumpore zeolites often have average pore diameters in a range of from about5 Å to about 7 Å. Combinations of zeolitic supports can be used.

Additional representative examples of zeolites that can be used as solidsupports herein include, for instance, a ZSM-5 zeolite, a ZSM-11zeolite, a EU-1 zeolite, a ZSM-23 zeolite, a ZSM-57 zeolite, an ALPO4-11zeolite, an ALPO4-41 zeolite, a Ferrierite framework type zeolite, andthe like, or any combination thereof.

In the supported chromium precursor, the solid support, the supportedchromium catalyst, and the reduced chromium catalyst, the zeolite can bebound with a support matrix (or binder), non-limiting examples of whichcan include silica, alumina, magnesia, boria, titania, zirconia, variousclays, and the like, including mixed oxides thereof, as well as mixturesthereof. For example, the supported chromium precursor, the solidsupport, the supported chromium catalyst, and the reduced chromiumcatalyst can comprise a binder comprising alumina, silica, a mixed oxidethereof, or a mixture thereof. The zeolite can be bound with the binderusing any method known in the art. While not being limited thereto, thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst can comprise a zeolite andfrom about 3 wt. % to about 35 wt. % binder; alternatively, from about 5wt. % to about 30 wt. % binder; or alternatively, from about 10 wt. % toabout 30 wt. % binder. These weight percentages are based on the totalweight of the respective supported chromium precursor, solid support,supported chromium catalyst, and reduced chromium catalyst.

In some aspects herein, the supported chromium precursor, the supportedchromium catalyst, and the reduced chromium catalyst can comprise aclay, an activated carbon, or a combination thereof, as the solidsupport.

It is worth noting that chromium polymerization catalysts usuallyrequire chromium loadings in a rather narrow range, typically from 0.5to 2 wt. %, because higher amounts degrade the polymer and lower amountsresult in low activity. However, no such limitation exists in thepresent invention. Thus, the amount of chromium in the supportedchromium catalyst and the reduced chromium catalyst typically can rangefrom about 0.01 to about 50 wt. %; alternatively, from about 0.01 toabout 10 wt. %; alternatively, from about 0.1 to about 15 wt. %;alternatively, from about 0.1 to about 0.5 wt. %; alternatively, fromabout 0.2 to about 10 wt. %; alternatively, from about 0.5 to about 2.5wt. %; alternatively, from about 2 to about 30 wt. %; or alternatively,from about 3 to about 15 wt. %. These weight percentages are based onthe amount of chromium relative to the total weight of the supportedchromium catalyst or the reduced chromium catalyst. While not wishing tobe bound by theory, it is believed, and the examples below seem toindicate, that lower chromium loadings (e.g., 1 wt. % and less) canresult in higher selectivity to a particular alcohol compound (orcarbonyl compound), while higher chromium loadings (e.g., 5-15 wt. % andabove) can result in higher alcohol and/or carbonyl yields per gram ofcatalyst.

Likewise, the amount of chromium in an average oxidation state of +5 orless in the reduced chromium catalyst is not particularly limited, andcan fall within the same ranges. Thus, the reduced chromium catalyst cancontain from about 0.01 to about 50 wt. %, from about 0.01 to about 10wt. %, from about 0.1 to about 15 wt. %, from about 0.1 to about 0.5 wt.%, from about 0.2 to about 10 wt. %, from about 0.5 to about 2.5 wt. %,from about 2 to about 30 wt. %, or from about 3 to about 15 wt. % ofchromium in an average oxidation state of +5 or less, based on theweight of the reduced chromium catalyst.

Generally, at least about 10 wt. % of the chromium in the supportedchromium catalyst is present in a hexavalent oxidation state before thereduction step, and more often at least about 20 wt. % is present aschromium (VI). In further aspects, at least about 40 wt. %, at leastabout 60 wt. %, at least about 80 wt. %, at least about 90 wt. %, or atleast about 95 wt. %, of the chromium in the supported chromium catalystcan be present in an oxidation state of +6. These weight percentages arebased on the total amount of chromium. Traditional chromium (VI)catalysts often will have an orange, yellow, or tan color, indicatingthe presence of chromium (VI).

Conversely, less than or equal to about 50 wt. % of the chromium in thereduced chromium catalyst is typically present in an oxidation state of+6 (VI), and more often less than or equal to about 40 wt. %. In furtheraspects, less than or equal to about 30 wt. %, or less than or equal toabout 15 wt. % of chromium in the reduced chromium catalyst can bepresent in an oxidation state of +6. The minimum amount of chromium (VI)often can be 0 wt. % (no measurable amount), at least about 0.5 wt. %,at least about 1 wt. %, at least about 2 wt. %, or at least about 5 wt.%. These weight percentages are based on the total amount of chromium.The reduced chromium catalysts often will have a green, blue, gray, orblack color.

Thus, the irradiation of the supported chromium catalyst—in the presenceof the hydrocarbon reactant—ordinarily results in at least about 10 wt.%, at least about 20 wt. %, at least about 40 wt. %, at least about 60wt. %, at least about 80 wt. %, or at least about 90 wt. %, of thesupported chromium catalyst being reduced or converted to form thereduced chromium catalyst.

Additionally or alternatively, the chromium in the reduced chromiumcatalyst can be characterized by an average valence of less than orequal to about 5.25. More often, the chromium in the reduced chromiumcatalyst has an average valence of less than or equal to about 5;alternatively, an average valence of less than or equal to about 4.75;alternatively, an average valence of less than or equal to about 4.5;alternatively, an average valence of less than or equal to about 4.25;or alternatively, an average valence of less than or equal to about 4.

It is important to note that chromium polymerization catalysts requiresupports of high porosity so as to allow fragmentation of the catalystand subsequent egress of the polymer chains, which are hundreds of timeslonger than the pore diameter in the catalyst. However, in the presentinvention, no such restriction exists. Thus, the total pore volume ofthe supported chromium precursor, the solid support, the supportedchromium catalyst, and the reduced chromium catalyst is not particularlylimited. For instance, the supported chromium precursor, the solidsupport, the supported chromium catalyst, and the reduced chromiumcatalyst can have a total pore volume in a range from about 0.1 to about5 mL/g, from about 0.15 to about 5 mL/g, from about 0.1 to about 3 mL/g,from about 0.5 to about 2.5 mL/g, or from about 0.1 to about 0.8 mL/g.Likewise, the surface area of the supported chromium precursor, thesolid support, the supported chromium catalyst, and the reduced chromiumcatalyst is not limited to any particular range. Generally, however, thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst can have a BET surface areain a range from about 50 to about 2000 m²/g, from about 50 to about 700m²/g, from about 50 to about 400 m²/g, from about 600 to about 1200m²/g, from about 150 to about 525 m²/g, or from about 200 to about 400m²/g.

The supported chromium precursor, the solid support, the supportedchromium catalyst, and the reduced chromium catalyst can have anysuitable shape or form, and such can depend on the type of process thatis employed to convert the hydrocarbon reactant into the alcoholcompound and/or carbonyl compound (e.g., fixed bed versus fluidizedbed). Illustrative and non-limiting shapes and forms include powder,round or spherical (e.g., a sphere), ellipsoidal, pellet, bead,cylinder, granule (e.g., regular and/or irregular), trilobe, quadrilobe,ring, wagon wheel, monolith, and the like, as well as any combinationthereof. Accordingly, various methods can be utilized to prepare thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst particles, including, forexample, extrusion, spray drying, pelletizing, marumerizing,spherodizing, agglomeration, oil drop, and the like, as well ascombinations thereof.

In some aspects, the supported chromium precursor, the solid support,the supported chromium catalyst, and the reduced chromium catalyst havea relatively small particle size, in which representative ranges for theaverage (d50) particle size of the supported chromium catalyst and thereduced chromium catalyst can include from about 10 to about 500microns, from about 25 to about 250 microns, from about 20 to about 100microns, from about 40 to about 160 microns, or from about 40 to about120 microns.

In other aspects, the supported chromium precursor, the solid support,the supported chromium catalyst, and the reduced chromium catalyst canbe in the form of pellets or beads—and the like—having an average sizeranging from about 1/16 inch to about ½ inch, or from about ⅛ inch toabout ¼ inch. As noted above, the size of the catalyst particles can bevaried to suit the particular process for converting the hydrocarbonreactant into the alcohol compound and/or carbonyl compound.

Supported catalysts also are encompassed herein. In one aspect, a firstsupported catalyst can comprise a solid support and a chromate compoundin an amount from about 0.1 to about 25 wt. % of chromium, based on theweight of the catalyst. Illustrative and non-limiting examples ofsuitable chromate compounds include potassium chromate, sodium chromate,ammonium chromate, potassium dichromate, sodium dichromate, ammoniumdichromate, and the like, as well as any combination thereof. In anotheraspect, a second supported catalyst can comprise a solid support, fromabout 0.1 to about 25 wt. % of chromium, and from about 0.1 to about 25wt. % of an alkali metal, based on the weight of the catalyst, whereinat least one bonding site on the chromium has a ligand characterized bythe following formula: —O-Hydrocarbon group (for example, an alkoxygroup can be bonded to the chromium). Typically, the molar ratio of thehydrocarbon group to chromium in the second supported catalyst can befrom about 0.25:1 to about 2:1, from about 0.5:1 to about 2:1, fromabout 0.5:1 to about 1.5:1, from about 0.75:1 to about 1.75:1, or fromabout 0.75:1 to about 1.25:1. Additionally or alternatively, the secondsupported catalyst can comprise chromium having an average valence ofless than or equal to about 5.25 in one aspect, less than or equal toabout 5 in another aspect, less than or equal to about 4.75 in anotheraspect, less than or equal to about 4.5 in another aspect, less than orequal to about 4.25 in yet another aspect, or less than or equal toabout 4 in still another aspect. These first and second supportedcatalysts also can have any of the features provided below and in anycombination.

The solid support for the first and second supported catalysts cancomprise any solid support disclosed herein, such as a solid oxide(e.g., silica, silica-titania, or silica-coated alumina), achemically-treated solid oxide (e.g., sulfated alumina or fluoridedsilica-coated alumina), a zeolite, a clay, an activated carbon, or anycombination thereof. In a particular aspect, the solid support cancomprise a silica-coated alumina, which can have any weight ratio ofalumina to silica disclosed herein, including from 1:20 to about 20:1,from about 1:5 to about 5:1, from about 3:1 to about 1:3, from about 1:1to about 3:1, from about 1:1 to about 2:1, from about 1.2:1 to about1.8:1, and the like.

The amount of chromium in the first and second supported catalysts isnot particularly limited, but often ranges from about 0.1 to about 25wt. %. Therefore, suitable ranges include from about 0.25 to about 15wt. %, from about 0.5 to about 5 wt. %, from about 2 to about 20 wt. %,or from about 3 to about 15 wt. % of chromium, based on the weight ofthe respective supported catalyst. Likewise, the amount of alkali metalis not particularly limited, but the first and second supportedcatalysts typically contain (based on the weight of the respectivecatalyst) from about 0.1 to about 25 wt. % alkali metal; alternatively,from about 0.25 to about 15 wt. % alkali metal; alternatively, fromabout 0.5 to about 5 wt. % alkali metal; alternatively, from about 2 toabout 20 wt. % alkali metal; or alternatively, from about 3 to about 15wt. % alkali metal.

Examples 1-67

The invention is further illustrated by the following examples, whichare not to be construed in any way as imposing limitations to the scopeof this invention. Various other aspects, modifications, and equivalentsthereof, which after reading the description herein, can suggestthemselves to one of ordinary skill in the art without departing fromthe spirit of the present invention or the scope of the appended claims.

Catalyst A was a Cr/silica catalyst containing 1 wt. % Cr, with a BETsurface area of 500 m²/g, a pore volume of 1.6 mL/g, and an averageparticle size of 100 μm. Prior to use, the catalyst was calcined in airat 650° C. for 3 hr to form the chromium (VI)/silica catalyst containing0.97 wt. % hexavalent Cr.

Catalyst B was a Cr/silica-titania catalyst containing 1 wt. % Cr and4.2 wt. % TiO₂, with a BET surface area of 500 m²/g, a pore volume of2.5 mL/g, and an average particle size of 130 μm. Prior to use, thecatalyst was calcined in air at 850-870° C. for 3 hr to form thechromium (VI)/silica-titania catalyst containing 0.95 wt. % hexavalentCr.

Catalyst C was a Cr/silica containing 10 wt. % Cr, the silica having aBET surface area of 500 m²/g, a pore volume of 1.6 mL/g, and an averageparticle size of 100 μm. Prior to use, the catalyst was calcined in airat 400° C. for 3 hr to form the chromium (VI)/silica catalyst containing5 wt. % hexavalent Cr.

Catalyst D was a Cr/silica-titania containing 0.8 wt. % Cr and 7.5 wt. %TiO₂, with a BET surface area of 550 m²/g, a pore volume of 2.5 mL/g,and an average particle size of 130 μm. Prior to use, the catalyst wascalcined in air at 850° C. for 3 hr to form the chromium(VI)/silica-titania catalyst containing 0.8 wt. % hexavalent Cr.

Catalyst E was a Cr/silica containing 0.28 wt. % Cr, with a BET surfacearea of 500 m²/g, a pore volume of 1.6 mL/g, and an average particlesize of 100 μm. Prior to use, the catalyst was calcined in air at 750°C. for 3 hr to form the chromium (VI)/silica catalyst containing 0.28wt. % hexavalent Cr.

Catalyst F was a Cr/silica containing 5 wt. % Cr, with a BET surfacearea of 500 m²/g, a pore volume of 1.6 mL/g, and an average particlesize of 100 μm. Prior to use, the catalyst was calcined in air at 500°C. for 3 hr to form the chromium (VI)/silica catalyst containing 4 wt. %hexavalent Cr.

Catalysts G1-G2 were prepared by dissolving CrO₃ in water, thenimpregnating the resulting solution onto an alumina (boehmite) with aBET surface area of 300 m²/g and a pore volume of 1.3 mL/g to equal 5wt. % Cr. After drying and prior to use, the catalysts were calcined inair at 500° C. (G1) or 600° C. (G2) for 3 hr to form the chromium(VI)/alumina catalysts containing 4.5 wt. % hexavalent Cr.

Catalysts H1-H2 were prepared by dissolving CrO₃ in water, thenimpregnating the resulting solution onto a silica-coated alumina (40 wt.% silica, BET surface area of 450 m²/g, pore volume of 1.4 mL/g, averageparticle size of 25 μm) to equal 5 wt. % Cr. After drying and prior touse, the catalysts were calcined in air at 500° C. (H1) or 600° C. (H2)for 3 hr to form the chromium (VI)/silica-coated alumina catalysts.

Catalyst J was prepared by dissolving K₂Cr₂O₇ in water, thenimpregnating the resulting solution onto a silica (BET surface area of500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) toequal 5 wt. % Cr. After drying and prior to use, the catalyst wascalcined in air at 500° C. for 3 hr to form the chromium (VI)/silicacatalyst containing 5 wt. % hexavalent Cr.

Catalyst K was prepared by dissolving K₂Cr₂O₇ in water, thenimpregnating the resulting solution onto a silica (BET surface area of500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) toequal 10 wt. % Cr. After removing excess water, the catalyst was heattreated in air at 100° C. for 3 hr to form the chromium (VI)/silicacatalyst containing 10 wt. % hexavalent Cr.

Catalyst L was prepared by dissolving K₂Cr₂O₇ in water, thenimpregnating the resulting solution onto a silica (BET surface area of500 m²/g, pore volume of 1.6 mL/g, average particle size of 100 μm) toequal 10 wt. % Cr. After removing excess water, the catalyst was heattreated in air at 200° C. for 3 hr to form the chromium (VI)/silicacatalyst containing 10 wt. % hexavalent Cr.

BET surface areas can be determined using the BET nitrogen adsorptionmethod of Brunauer et al., J. Am. Chem. Soc., 60, 309 (1938) asdescribed in ASTM D1993-91. Total pore volumes can be determined inaccordance with Halsey, G. D., J. Chem. Phys. (1948), 16, pp. 931. Thed50 particle size, or median or average particle size, refers to theparticle size for which 50% of the sample by volume has a smaller sizeand 50% of the sample has a larger size, and can be determined usinglaser diffraction in accordance with ISO 13320.

Table I summarizes the reactions of Examples 1-67, in which thesupported chromium catalyst was first charged to an air-tight glasscontainer at 25° C. (or a different temperature if specified), followedby the addition of the hydrocarbon reactant. The glass container wasthen exposed to a light source as noted in Table I. For all exampleswhere the glass container was exposed to light, the container was slowlyrotated at 5-10 rpm to turn over the catalyst particles in the bottle toensure even exposure of the mixture of the supported chromium catalystand the hydrocarbon reactant to each other and to the light. Samplesexposed to sunlight were taken outside and placed in direct sunlight.For examples where the glass container was exposed to artificial light,the sample was placed in a box containing a fluorescent light or a LEDlight, where three 15 watt bulbs were placed in a plane about 3 inchesapart and about 2 inches from the bottle. Reduction of the supportedchromium catalysts was monitored by the presence of a color change. Eachsupported chromium catalyst comprising chromium in the hexavalentoxidation state had an orange color which darkened significantly uponexposing the supported chromium catalyst to light in the presence of thehydrocarbon reactant, and usually assuming a green or blue color,indicating reduction of the supported chromium catalyst startingmaterial, and formation of the reduced chromium catalyst.

After the desired exposure time, the reduced chromium catalyst was mixedwith a hydrolysis agent to cleave the hydrocarbon-containing ligand fromthe reduced chromium catalyst. The mixture was stirred for severalminutes. The hydrolysis agent used was generally selected so as to notinterfere with analysis of the reaction product (e.g., methanol was notused as the hydrolysis agent when the reaction product after hydrolysiscould contain methanol, etc.).

Table I summarizes the results of Examples 1-67, and lists the specificsupported chromium catalyst and amount, the hydrocarbon reactant andamount, the light treatment and resulting color, the hydrolysis agentand amount, the acid/Cr (molar), alcohol/Cr (molar), the GC-MS/Cr(molar), the total/Cr (molar), and an analysis of the reaction product(oxygenated products) after hydrolysis. The reaction product analysisincludes only oxygen-containing products that were derivable from thereductant/reactant and does not include, for example, materialsresulting from the hydrolysis agent or its by-products, or oligomersresulting from polymerization. For the oxygenated reaction products,area % from the analytical procedures listed below is roughly equivalentto mol %, thus the results in Table I are shown in mol %.

Carboxylic acid products (and acid/Cr ratios on a molar basis) weredetermined by first neutralizing the product acids with a solution ofsodium hydroxide to put them into the ionic form. Then, a small amountof the sample was injected through an ion column designed to separateanions from weak organic acids through an ion chromatography process. ADionex IC-3000 instrument with an ICE-AS1 column and guard was used. Thetest was specifically sensitive to linear carboxylic acids from C₁ toC₆, glutarate and glycolate ions. Results were reported in micrograms ofcarboxylate per mL of solution, which was then converted to moles.

Lower alcohol products (and alcohol/Cr on a molar basis) were determinedusing a GC-MS procedure, with an Agilent 6890 gas chromatograph having aflame-ionizing detector (FID). It used a Restek Stapilwax column (P/N10658) designed and gated specifically to separate and detect lightalcohols. The procedure was gated for acetone, methanol, ethanol,isopropanol, n-propanol, isobutanol, n-butanol, t-butanol, 2-butanol,2-butoxyethanol, acetonitrile and tetrahydrofuran.

Additional reaction products (and GC-MS/Cr on a molar basis) weredetermined using another GC-MS procedure, as follows. Gas chromatographywas performed using an Agilent 7890B GC equipped with both flameionizing and mass spectral analysis. An all-purpose capillary column(Agilent J&W VF−5 ms, 30 m×0.25 mm×0.25 μm) was used with variabletemperature. Approximate 0.5 μL sample aliquots were injected into a GCport held at 250° C. using a split ratio of 10:1. The carrier gas wasultra-high purity helium and was electronically controlled throughoutthe run to a constant flow rate of 1.2 mL/min. Initial columntemperature was held at 50° C. for 5 min, ramped at 20° C./min to 250°C., and then held at 250° C. for 19 min. Spectral assignment was madevia mass correlation using an Agilent 5977B mass spectrometer connectedto the GC unit using electron ionization at 70 eV. The nominal massrange scanned was 14-400 m/z using a scan time of 0.5 sec. Nominaldetector voltage used was 1200 V. For calibration purposes both the FIDand MS detectors were sometimes used in sequence on the same orreference samples.

Due to the wide range of oxygenated products produced herein, one or allof these three procedures were used to characterize the reaction productafter hydrolysis. In some cases, the same compound was detected by morethan one technique, and this was subtracted out of the total/Cr (on amolar basis) to prevent double counting of the same compound by morethan one analytical technique. For the most part, however, there wasvery little overlap between the three analytical procedures.

Referring now to the data in Table I, Examples 1-10 demonstrate theunexpected conversion of methane into methanol at ambient temperatureusing a variety of supported chromium catalysts, irradiation treatments,and hydrolysis agents. Note that Examples 1-4 used only one analyticaltechnique and showed a product stream that was 100% methanol, whereasExamples 6-10 used all three analytical techniques and resulted inproduct streams containing 66-97 mol % methanol, the balance beingformic acid.

Similar successful results were found for the conversion of ethane intoethanol, isobutane into t-butanol/i-butanol, n-pentane into2-pentanol/1-pentanol, cyclopentane into cyclopentanol, n-hexane intovarious hexanols, cyclohexane into cyclohexanol, and toluene intobenzaldehyde/benzyl alcohol. When the hydrocarbon reactant wasi-pentane, the oxygenated reaction product contained a variety ofalcohol and carbonyl products, whereas when the reactant wasdichloromethane, no conversion to an alcohol or carbonyl was noted.While the focus of these examples was not to maximize chromiumconversion (or yield to any particular alcohol or carbonyl compound),the total/Cr molar value in Table I illustrates that significantchromium conversion and alcohol/carbonyl yield can be achieved,depending of course on the reductant, the catalyst (and chromiumloading), and the irradiation conditions, among other factors.

When the reactant was an olefin, it was found that the GC-MS analyticaltechnique was necessary to identify diol products, thus examples inwhich this technique was not used may give an incomplete representationof the oxygenated product mix. Generally, examples that utilizedethylene as the reductant formed a reaction product (even when used at−78° C. to prevent polymerization) after hydrolysis that includedethanediol and methanol, ethanol, formic acid, and/or acetic acid. Thelower reaction temperatures seemed to favor selectivity to the diol.Examples that utilized 1-pentene as the reductant formed a reactionproduct (even with no light irradiation, see Example 44) afterhydrolysis that included a pentanediol (e.g., 1,2-pentanediol) andvarious acids and other alcohols. Examples that utilized 1-hexene or2-hexene as the reductant formed a reaction product (even with no lightirradiation, see Example 55) after hydrolysis that included a hexanediol(e.g., 1,2-hexanediol and/or 3,4-hexanediol) and various acids and otheralcohols. Table I demonstrates that these olefins are very reactive and,therefore, the reaction product typically contained a mixture ofmono-alcohols, diols, aldehydes, ketones, and/or carboxylic acids.

Of particular interest, and unexpectedly, the chromate catalysts(Catalysts J-L) very effectively converted hydrocarbons into alcoholsand/or carbonyls, despite low heat treatment temperatures (100-500° C.).Also, catalysts with high loadings of 5-10 wt. % chromium, such asCatalysts C and F-L, often had relatively low “total/Cr” molar yields,but when multiplied by a factor of 5-10 to compare to a 1 wt. % chromiumcatalyst, these high chromium catalysts produced an exceptional amountof alcohol and/or carbonyl products.

TABLE I Summary of Examples 1-67 (products in mol %) Example 1 2 3 4Catalyst A B A B Weight (g) 2.7 2.0 1.8 2.0 Reductant Methane MethaneMethane Methane Amount 10 psig 10 psig 10 psig 10 psig Light 4 hr Sun 4hr Sun 6 hr Sun 6 hr Sun Color Green Green Green Green HydrolysisH₂O/Ether H₂O/Ether H₂O H₂O Amount (mL) 20 20 20 20 Acid/Cr 0 0 0Alcohol/Cr 1.013 0.272 0.261 0.173 GC-MS/Cr Total/Cr 1.013 0.272 0.2610.173 Oxygenated methanol 100% methanol 100% methanol 100% methanol 100%Products Example 5 6 7 8 Catalyst D E J F Weight (g) 2.1 2.8 2.2 2.1Reductant Methane Methane Methane Methane Amount 15 psig 15 psig 15 psig15 psig Light 44 hr Blue 67 hr Blue 67 hr Blue 67 hr Blue Color Olivegreen Olive green Red-brown Dark brown-black Hydrolysis H₂O + CH₃CNH₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 15 15 Acid/Cr0.009 0.010 0.007 0.008 Alcohol/Cr 0.284 0.320 0.030 0.073 GC-MS/Cr0.007 0.000 0 0.025 Total/Cr 0.300 0.330 0.037 0.081 Oxygenated methanol 96% methanol  97% methanol  80% methanol  90% Products formic acid  4%formic acid  3% formic acid  20% formic acid  10% Example 9 10 11 12Catalyst H2 G2 D B Weight (g) 2.2 2.0 2.0 2.1 Reductant Methane MethaneDichloromethane Ethane Amount 15 psig 15 psig 0.5 mL 15 psig Light 67 hrBlue 67 hr Blue 7 hr Blue 72 hr Blue Color Dark brown Dark brown OliveGreen Blue-gray Hydrolysis H₂O + CH₃CN H₂O + CH₃CN 10% H₂O/MeOH H₂OAmount (mL) 15 15 40 20 Acid/Cr 0.003 0.002 0.042 Alcohol/Cr 0.025 0.0040.366 GC-MS/Cr 0.000 0.000 0.000 0.000 Total/Cr 0.028 0.006 0.000 0.408Oxygenated methanol  91% methanol  66% No Products ethanol  72% Productsformic acid  9% formic acid  34% Detected methanol  16% formic acid  6%hexanoic acid  3% acetic acid  1% pentanoic acid  1% Example 13 14 15 16Catalyst D D B B Weight (g) 1.9 2.5 2.6 1.9 Reductant Ethane i-Butanen-Pentane n-Pentane Amount 15 psig 10 psig 0.75 mL 0.75 mL Light 30 hrBlue 6 hr UV 1 hr UV 3.3 hr UV Color Blue-gray Green Blue-gray Blue-grayHydrolysis H₂O + CH₃CN 4% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH Amount (mL)15 15 12 12 Acid/Cr 0.013 0.000 Alcohol/Cr 0.374 0.258 GC-MS/Cr 0.0090.465 0.270 0.500 Total/Cr 0.383 0.723 0.270 0.500 Oxygenated ethanol 90% t-butanol  40% 2-pentanol  49% 2-pentanol  47% Products methanol 6% i-butanol  28% 2-pentanone  33% 2-pentanone  36% acetic acid  3%acetone  10% 1-pentanol  18% 1-pentanol  17% isopropanol  1% isopropanol 5% n-propanol  1% isobutanal  5% Example 17 18 19 20 Catalyst C D E DWeight (g) 1.9 2.0 2.6 2.0 Reductant n-Pentane n-Pentane n-Pentanen-Pentane Amount 0.5 mL 0.5 mL 2 mL 2 mL Light 3 hr Blue 7 hr Blue 26 hrUV 26 hr UV Color Black Blue-gray Blue-gray Blue-gray Hydrolysis 10%H₂O/MeOH Vitamin C 5% H₂O/MeOH 5% H₂O/MeOH Amount (mL) 11 30 10 10Acid/Cr 0.000 0.000 0.000 0.042 Alcohol/Cr 0.000 0.000 GC-MS/Cr 0.2071.140 0.143 0.499 Total/Cr 0.207 1.140 0.143 0.541 Oxygenated2-pentanone  62% 2-pentanol  63% 2-pentanol  41% 2-pentanol  39%Products 2-pentanol  14% 1-pentanol  19% 1-pentanol  23% 1-pentanol  21%3-pentanone  10% pentanal  18% 2-pentanone  21% 2-pentanone  15%3-penten-2-one  3% 3-pentanone  11% 3-pentanone  10% 1-pentanol  2%C10H18O  4% formic acid  8% 3-penten-2-one  2% 2-pentenal  2% Example 2122 23 24 Catalyst L D E D Weight (g) 3.0 1.9 2.3 1.1 Reductant n-Pentanei-Pentane i-Pentane i-Pentane Amount 2 mL 0.5 mL 0.5 mL 2 mL Light UV 24h 7 hr Blue 31 hr Blue 4.5 hr UV Color Brown Blue-gray Blue-grayGray-blue Hydrolysis 4% H₂O/MeOH 10% H₂O/MeOH H₂O + CH₃CN 5% H₂O/MeOHAmount (mL) 15 40 15 15 Acid/Cr 0.002 0.000 0.000 0.006 Alcohol/Cr 0.0050.347 GC-MS/Cr 0.077 0.850 0.929 0.600 Total/Cr 0.083 0.850 0.929 0.953Oxygenated 2-pentanol  40% t-pentanol  24% 2-pentanol  31% ethanol  27%Products 2-pentanone  21% 3-Me-2-butanol  23% acetic acid  23%2-Me-1-butanol  18% 1-pentanol  15% Me-butanol  22% 2-pentanol  22%t-pentanol  17% 3-pentanone  9% isoamyl alcohol  13% 3-pentanol  11%3-Me-2-butanol  10% isopropanol  4% 2-Me-butanal  11% C5H4O3  7% isoamylalcohol  9% C10H18O  2% 3-Me-2-butanone  7% isobutanol  8% C7H14O  2%3-Me-2-butanone  6% formic acid  2% C6H12O3  3% Example 25 26 27 28Catalyst J F H1 G1 Weight (g) 2.2 2.4 1.9 1.9 Reductant i-Pentanei-Pentane i-Pentane i-Pentane Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light31 hr Blue 31 hr Blue 40 hr Blue 40 hr Blue Color Dark redBlue-gray-black Green-brown Green-brown Hydrolysis H₂O + CH₃CN H₂O +CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 15 15 Acid/Cr 0.0040.004 0.004 0.016 Alcohol/Cr GC-MS/Cr 0.744 0.042 0.061 0.052 Total/Cr0.747 0.046 0.064 0.068 Oxygenated 2-Me-2-butanol  41% 3-Me-1-butanol 26% C5H12O alcohol  25% C5H12O alcohol  23% Products 3-Me-2-butanol 21% 2-Me-1-butanol  24% C5H8O aldehyde  22% 2-Me-2-butenal  23%2-Me-1-butanol  15% 2-Me-2-butenal  24% C5H120O  17% C5H12O2  13%3-Me-2-butanone  9% 3-Me-2-butenal  5% 3-Me-2-pentanone  5% formic acid 12% 3-Me-1-butanol  9% acetic acid  4% C5H12O2  5% C5H12O  12% C10/C11dioxygenate  2% C5H10O2  4% C6H10O  4% acetic acid  11% 4-OH-3-Me-2-formic acid  4% butanone  3% 2-pentenal  2% formic acid  3% C5H10O  3%3-Me-2 butenal  2% acetic acid  2% Example 29 30 31 32 Catalyst D B B BWeight (g) 2.1 2.1 1.2 1.5 Reductant Cyclopentane n-Hexane CyclohexaneDecalin Amount 0.5 mL 0.5 mL 0.5 g Light 7 hr Blue 3.3 hr UV 2 hr BlueLED 2 hr Blue LED Color Blue-gray Blue-gray Deep blue Light blueHydrolysis 10% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH 10% H₂O/MeOH Amount(mL) 40 12 12 12 Acid/Cr 0.000 No data No data Alcohol/Cr No data Nodata GC-MS/Cr 0.606 0.573 No data No data Total/Cr 0.606 0.573 decalols,Oxygenated cyclopentanol  85% 2-hexanol  25% cyclohexanol  49% C10H18O 77% decalones, Products cyclopentanone  15% 2-hexanone  23%cyclohexanone  40% C10H18O  17% 2-cyclohexen-1- 3-hexanol  20% one  7%C10H14O  2% 3-hexanone  17% cyclohexanediol  2% C10H14O2  1% 1-hexanol 15% C14H22O  1% naphthalenone  1% C6H10O2  1% Example 33 34 35 36Catalyst B B K A Weight (g) 1.1 1.6 3.3 2.0 Reductant Adamantane TolueneToluene Ethylene Amount 0.5 g 0.5 mL 2 mL 10 psig Light 2 hr Blue LED1.5 hr Blue UV 24 h 9 hr Sun Color Blue Blue-black Brown Blue-grayHydrolysis 10% H₂O/MeOH 10% H₂O/MeOH 4% H₂O/MeOH H₂O Amount (mL) 12 6 1520 Acid/Cr No data 0.001 0.096 Alcohol/Cr No data 0.003 0.108 GC-MS/CrNo data 0.567 0.129 Total/Cr 0.567 0.133 0.204 Oxygenated adamantanone 32% benzaldehyde  41% benzaldehyde  77% methanol  51% Productsadamantanol  25% benzyl alcohol  17% benzyl alcohol  20% formic acid 46% adamantan-2-ol  20% C14H12O  9% isopropanol  2% n-propanol  2%C1OH14O  16% benzophenone  8% formic acid  1% acetic acid  1%adamantanediol  2% C14H12O  6% C11H20O  1% C14H12O  6% 4-Me phenol  5%2-Me phenol  5% Example 37 38 39 40 Catalyst B D D D Weight (g) 2.1 2.42.1 2.1 Reductant Ethylene Ethylene Ethylene Ethylene Amount 10 psig 15psig (−78 C.) 15 psig (−78 C.) 15 psig (−78 C.) Light 9 hr Sun 60 hrBlue 24 hr Blue 24 hr Blue Color Blue-gray Blue-green Blue-greenBlue-green Hydrolysis 0.1N NaOH 0.1N NaOH 0.1N NaOH 0.1N NaOH Amount(mL) 20 15 15 15 Acid/Cr 0.233 0.110 0.136 0.144 Alcohol/Cr 0.101 0.1620.111 0.401 GC-MS/Cr 0.035 0.071 0.162 Total/Cr 0.335 0.272 0.318 0.675Oxygenated formic acid  68% formic acid  39% formic acid  48% ethanediol 72% Products methanol  28% methanol  29% ethanediol  25% formic acid 20% acetic acid  1% ethanediol  27% methanol  24% diethylene glycol  4%ethanol  1% ethanol  2% ethanol  2% methanol  2% acetic acid  1%n-propanol  1% acetic acid  1% n-propanol  1% propionic acid  1% ethanol 1% acetic acid  1% Example 41 42 43 44 Catalyst E D D D Weight (g) 2.32.0 1.5 2.1 Reductant Ethylene Ethylene 1-Pentene 1-Pentene Amount 15psig 15 psig 0.5 mL 0.5 mL Light 24 hr UV 24 hr UV 14 hr Blue Dark - 24hr Color Blue-gray Hydrolysis H₂O + CH₃CN H₂O + CH₃CN H₂O H₂O Amount(mL) 15 15 20 15 Acid/Cr 0.461 0.181 0.245 0.012 Alcohol/Cr 0.136 0.0690.044 GC-MS/Cr 0.017 0.190 1.047 0.016 Total/Cr 0.614 0.436 1.193 0.072Oxygenated acetic acid  38% formic acid  35% C8H18O  17% 1-butanol  29%Products formic acid  36% ethanediol  32% formic acid  13% formic acid 14% methanol  19% methanol  12% C10 or C11 alcohol  12% n-propanol  9%ethanediol  2% diethylene glycol  11% 1,2-pentanediol  7% ethanediol  8%ethanol  2% acetic acid  6% C9H20O  7% 1,2-pentandiol  8% n-propanol  1%ethanol  3% C8-C10 alcohol  6% methanol  8% 2-heptanone  5% 2-pentenal 7% C7H14O3  4% acetone  5% C10H22O  4% 2-penten-1-ol  3% isoamylalcohol  3% ethanol  2% acetic acid  3% 3-pentanol  2% Example 45 46 4748 Catalyst D D D D Weight (g) 2.0 1.9 1.7 1.5 Reductant 1-Pentene1-Pentene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 24hr UV 2 hr UV 7 hr Blue 14 hr Blue Color Magenta Sky blue Blue-grayBlue-gray Hydrolysis H₂O H₂O 10% H₂O/MeOH H₂O Amount (mL) 15 15 40 20Acid/Cr 0.015 0.018 0.036 0.248 Alcohol/Cr 0.000 0.091 GC-MS/Cr 0.0870.124 1.315 Total/Cr 0.102 0.233 0.036 1.548 Oxygenated 1,2-pentane diol 31% 1-butanol  20% formic acid 100% hexanoic acid  41% Products2-pentenal  13% 1,2-pentanediol  17% formic acid  10% formic acid  11%2-pentenal  11% 2-hexanone  8% C10H22O  10% n-propanol  7% 2-octanone 3% C5H10O2   5% ethanediol  7% 1,2-hexandiol  3% 2-heptanone   5%formic acid  6% 1-hexen-3-ol  3% ethyl ether propanoic  5% C8-11oxygenate  3% acid 3-penten-2-ol  3% C8-10 oxygenate  3% 2-penten-1-ol 5% Me-nonanol  2% C9-11 oxygenate  3% ethanol  3% Me-heptanol  2% C5di-oxygenate  2% 2-heptanone  2% butyric acid  2% C10H20O  2% methanol 2% 2-hexanol  2% 2-Me-2-pentenal  2% 2-hexenal  2% Example 49 50 51 52Catalyst D D D D Weight (g) 2.1 2.1 2.0 1.2 Reductant 1-Hexene 1-Hexene1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 2 mL Light 14 hr Blue 31hr Blue 31 hr Blue 4.5 hr UV Color Blue-gray Blue-gray Blue-grayBlue-green Hydrolysis Vitamin C H₂O + CH₃CN 0.1N HCl + Fe⁺² 5% H₂O/MeOHAmount (mL) 20 15 15 15 Acid/Cr 0.058 0.082 0.038 0.007 Alcohol/Cr 0.198GC-MS/Cr 0.426 0.153 0.095 0.458 Total/Cr 0.426 0.235 0.133 0.663Oxygenated 1-hexene-3-ol  19% formic acid  35% formic acid  28% ethanol 22% Products hexanoic acid  14% 1-hexen-3-ol  18% 1-hexen-3-ol  24%2-hexen-1-ol  15% 1,2-hexanediol  14% 1,2-hexanediol  12% 1,2-hexanediol 18% 1-hexen-3-ol  13% C6 oxygenate  10% C6H14O2-Si  8% C6H12O  9%3-hexanone  11% formic acid  9% 2-hexenal  6% 2-hexenal  9% 2-hexenal 10% 2-hexen-1-ol  7% dimethylbutanol  4% 2-hexen-1-ol  7% 2-hexanol  9%C5/C6 oxygenate  6% 2-hexene-1-ol  4% 2-hexanol  5% n-propanol  7%acetic acid  5% 2-octanone  3% 2-hexanone  6% 2-hexanone  2%1,2-hexanediol  5% hexanal  2% C6H12O  2% 2-hexanol  2% Example 53 54 5556 Catalyst E D D D Weight (g) 2.0 1.6 2.2 2.0 Reductant 1-Hexene1-Hexene 1-Hexene 1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 24hr UV 2 hr UV Dark - 24 hr 24 hr UV Color Blue-gray Magenta HydrolysisH₂O + CH₃CN H₂O H₂O H₂O Amount (mL) 15 10 15 15 Acid/Cr 0.127 0.0110.011 0.011 Alcohol/Cr 0.069 0.021 0.010 0.013 GC-MS/Cr 0.012 0.0400.163 0.134 Total/Cr 0.208 0.072 0.184 0.159 Oxygenated acetic acid  58%1.2-hexanediol  26% 1-hexen-3-ol  28% 1-hexen-3-ol  19% Productsmethanol  13% formic acid  15% 2-hexenal  17% 1,2-hexanediol  15%ethanol  10% ethanol  14% 1,2-hexanediol  13% 2-hexenal  12% 1-butanol 7% isobutanol  12% C6H12O  8% 2-hexanone  9% 1,2-hexanediol  6% C6H14O 7% C6H12O  7% 2-hexen-1-ol  6% formic acid  4% C9/C10 oxygenate  6%2-hexen-1-ol  6% formic acid  6% n-propanol  3% 1-hexanol  3% formicacid  5% C6H12O  5% dimethylbutanoic 1-butanol  3% acid  5% C6H12O2  4%1-pentanol  2% 1-butanol  3% hexenal  4% 2-hexanone  2% 3-Me-2-pentanone 2% 1-butanol  4% C6H14O  3% 2-hexanol  3% Example 57 58 59 60 CatalystD J F H1 Weight (g) 2.0 2.6 2.8 1.9 Reductant 1-Hexene 1-Hexene 1-Hexene1-Hexene Amount 0.5 mL 0.5 mL 0.5 mL 0.5 mL Light 2 hr UV 31 hr Blue 31hr Blue 40 hr Blue Color Sky blue Dark red Blue-gray-black Green-brownHydrolysis H₂O H₂O + CH₃CN H₂O + CH₃CN H₂O + CH₃CN Amount (mL) 15 15 1515 Acid/Cr 0.012 0.010 0.001 0.003 Alcohol/Cr 0.014 GC-MS/Cr 0.102 0.4960.794 0.155 Total/Cr 0.127 0.506 0.795 0.158 Oxygenated 1-hexen-3-ol 23% 1,2-hexanediol  37% 1,2-hexanediol  20% 3,4-hexandiol  9% Products2-hexenal  15% 1-hexen-3-ol  14% 1-hexen-3-one  20% C6H10O ketone  9%1,2-hexandiol  10% 5-hexen-2-ol  14% 2-hexenal  13% 2-hexanol  9%butanoic acid ethyl formic acid  8% 5-hexen-3-ol  11% ester  11% C6H12Oalcohol  8% C6H12O  7% ethyl butanoate  5% 2-hexen-1-ol  7% 1-hexen-3-ol 8% C6H12O  7% 1-pentanol  4% 2-hexanone  4% 2,3 hexanediol  7%2-hexen-1-ol  4% 2-hexen-1-ol  4% 1-hexen-3-ol  3% C6H12O alcohol  7%1-butanol  4% 5-hexen-1-ol  4% C6H12O alcohol  3% C6H10O ketone  5% diMebutanoic acid  4% C6H12O  2% hexanediol  3% 2-hexanone  5% isobutanol 3% C6H12O  1% 2-hexen-1-ol  3% 2-hexenal  4% 2-hexen-1-ol  2% 2-hexenal 1% 3-hexen-2-one  3% 1,2-hexanediol  2% Example 61 62 63 64 Catalyst G1K L D Weight (g) 2.1 2.9 2.7 1.9 Reductant 1-Hexene 1-Hexene 1-Hexene2-Hexene Amount 0.5 mL 2 mL 2 mL 0.5 mL Light 40 hr Blue UV 24 h UV 24 h14 hr Blue Color Green-brown Brown Brown Blue-gray Hydrolysis H₂O +CH₃CN 4% H₂O/MeOH 4% H₂O/MeOH H₂O Amount (mL) 15 15 15 20 Acid/Cr 0.0120.003 0.003 0.145 Alcohol/Cr 0.003 0.004 GC-MS/Cr 0.147 0.025 0.0512.318 Total/Cr 0.159 0.031 0.058 2.462 Oxygenated 1-hexen-3-ol  18%5-hexen-2-ol  21% 5-hexen-2-ol  17% 2,3-hexanediol  21% Products C6H12O 10% 5-hexen-2-one  16% 5-hexene-ol  13% 3-hexen-2-one  17%1,2-hexanediol  9% 5-hexen-3-ol  15% 1-hexen-3-ol  10% 4-hexen-3-one 11% C6H12O  8% 1-hexen-3-ol  7% 5-hexen-2-one  9% 3,4-hexanediol  8%2-hexanol  8% isopropanol  7% 1-pentanol  6% 4-hexen-3-ol  8% C6H12O  7%formic acid  7% C11/12 oxygenate  4% 2-Me-1-penten-3-ol  8% C6H14O2  7%1-pentanol  7% formic acid  4% 1-hexen-3-ol  5% 2,3-hexanediol  5%5-hexene-ol  7% isopropanol  4% 2-hexenal  3% C6H12O  4% 4-hexen-3-one 4% 5-hexen-1-ol  3% formic acid  3% acetic acid  3% ethanol  3% C10-12oxygenate  3% C6H12O  2% 2-hexen-1-ol  3% 2-hexenal  3% 1,2-hexandiol 3% 2-butenal  2% formic acid  3% pentanal  3% 4-hexen-1-ol  2% Example65 66 67 Catalyst D D D Weight (g) 2.3 2.2 2.0 Reductant n-Pentanen-Pentane n-Pentane Amount 0.25 mL 1 mL 3 mL Light UV 24 hr UV 24 hr UV24 hr Color Dark blue-gray Green Dark blue-gray Hydrolysis 5% H₂O/MeOH5% H₂O/MeOH 5% H₂O/MeOH Amount (mL) 15 15 15 Acid/Cr 0.013 0.011 0.012Alcohol/Cr GC-MS/Cr 0.323 1.819 1.074 Total/Cr 0.336 1.831 1.086Oxygenated 2-pentanol  46% 2-pentanol  39% 2-pentanol  62% Products1-pentanol  21% 1-pentanol  16% 2-pentanone  18% 2-pentanone  13%2-pentanone  13% 3-pentanone  9% 3-pentanone  6% 3-pentanone  6%1-pentanol  3% 2-hexenal  5% C5H10O  4% 2-pentenal  2% formic acid  3%C10H18O  2% 3-penten-2-one  2% 2-pentenal  2% C7H12O  2% C7H12O  2%2-Me-2-butenal  2% C8H14O  1% formic acid  1%

Examples 68-74

Examples 68-74 were performed to determine the extent of reduction ofthe hexavalent chromium and the average valence after reduction in arepresentative supported chromium catalyst. Table II summarizes theresults. Example 74 was a chromium/silica-titania catalyst containingapproximately 0.8 wt. % chromium and 7 wt. % titania, and having a BETsurface area of 530 m²/g, a pore volume of 2.6 mL/g, and an averageparticle size of 130 um, which was calcined in dry air at 850° C. for 3hr to convert chromium to the hexavalent oxidation state (orange). Thisconverted over 86 wt. % of the chromium into the hexavalent state. ForExamples 68-69, approximate 2 g samples of the catalyst of Example 74were separately charged to a glass reaction vessel and 0.5 mL of liquidisopentane was charged to the vessel. For Examples 70-71, about 1.5 atmof gaseous ethane was charged to the glass bottle. Then, the bottle wasplaced in a light-proof box under blue fluorescent light (approximately2 times the intensity expected from sunlight), and the bottle wascontinuously rotated so that all of the catalyst was exposed to thelight for 24 hr. The final catalyst color is noted in Table II.Afterward, into the bottle, along with the catalyst, was introducedabout 20 mL of a solution of 2 M H₂SO₄. To this was added 5 drops offerroin Fe(+3) indicator. This usually turned a blue-green colorindicating the presence of Fe(III) ions. Next, the solution was titratedto the ferroin endpoint (red color) using a solution of ferrous ammoniumsulfate, which had been previously calibrated by reaction with astandardized 0.1 M sodium dichromate solution. When the solution turnedred, the end point was signaled, and the titrant volume was recorded, tocalculate the oxidation capacity of the catalyst, expressed as wt. %Cr(VI) and as percent reduced, that is, the percent of the originalCr(VI) oxidative power that has been removed by the reduction treatment.The average valence was also computed by multiplying the percent reducedby +3 and subtracting that number from +6.

Of course, this treatment gives only an average oxidation state. Notethat although Table II lists the oxidative power measured as wt. %Cr(VI), in reality all of the chromium could be present in lower valencestates, such as Cr(IV) or Cr(V). Thus, the Cr(VI) value in Table II onlylists the maximum amount of Cr(VI) that could be present. More likely,the reduced chromium catalysts have a combination of several valencestates that produce the measured oxidative power. Note that some of thereduced chromium, and particularly those catalysts reduced with CO, maybe in the divalent state, which would not have been detected in thistest, which stops in the trivalent state.

Example 74 demonstrates that the air-calcined chromium catalystcontained substantially most of its chromium (0.69/0.80=86 wt. %)present as Cr(VI), and it is this Cr(VI) amount that is being reduced inthe light treatment. Therefore, this amount of Cr(VI) serves as thestarting amount, which had an average valence of +6, and which serves asa reference, to which the reduced catalysts are then compared. Examples68-69 were reduced chromium catalysts with an average valence ofapproximately +3.3, with no more than 0.06 wt. % Cr(VI), and with lessthan 10 wt. % of the starting hexavalent chromium still remaining in thehexavalent oxidation state. Examples 70-71 were reduced chromiumcatalysts with an average valence of approximately +4.1, with no morethan 0.26 wt. % Cr(VI), and with less than 40 wt. % of the chromium inthe hexavalent oxidation state. For Examples 72-73, the supportedchromium catalyst was reduced in CO with either blue light or elevatedtemperature, resulting in no oxidative power being measured (0 wt. %Cr(VI) in the table). Thus, the average valence must be no more than +3.But the supported chromium catalyst that was CO-reduced by conventionalmeans (Example 73) is known to have a valence of mostly Cr(II) afterreduction, which is not detected in this test. Accordingly, Examples 72and 73 are listed as less than or equal to +3. Notably, this test cannotdistinguish between Cr(II) and Cr(III) species, but there was nomeasurable amount of hexavalent chromium in Examples 72-73.

TABLE II Examples 68-74 Aver- Ex- Cr Re- age am- Treat- Catalyst (VI)duced Va- ple Reductant ment Color (g) (wt. %) (wt. %) lence 68isopentane Blue blue 2.05 0.06 90.8 3.28 light 24 hr 69 isopentane Blueblue 2.08 0.06 90.9 3.27 light 24 hr 70 ethane Blue olive 2.14 0.26 62.34.13 light green 24 hr 71 ethane Blue olive 2.30 0.26 61.9 4.14 lightgreen 24 hr 72 CO Blue blue 2.33 0.00 100 ≤3 light green 24 hr 73 CO COblue 2.52 0.00 100 ≤3 re- duction 30 min- 350° C. 74 None None orange —0.69 0 6.00

The invention is described above with reference to numerous aspects andspecific examples. Many variations will suggest themselves to thoseskilled in the art in light of the above detailed description. All suchobvious variations are within the full intended scope of the appendedclaims. Other aspects of the invention can include, but are not limitedto, the following (aspects are described as “comprising” but,alternatively, can “consist essentially of” or “consist of”):

Aspect 1. A process for converting a hydrocarbon reactant into analcohol compound and/or a carbonyl compound, the process comprising:

(a)(i) heat treating a supported chromium precursor at a peaktemperature from about 50° C. to about 1000° C. to form a supportedchromium catalyst comprising chromium in a hexavalent oxidation state;or

(a)(ii) contacting a chromium precursor with a solid support while heattreating at a peak temperature from about 50° C. to about 1000° C. toform a supported chromium catalyst comprising chromium in a hexavalentoxidation state; or

(a)(iii) heat treating a solid support at a peak temperature from about50° C. to about 1000° C. and then contacting a chromium precursor withthe solid support to form a supported chromium catalyst comprisingchromium in a hexavalent oxidation state;

(b) irradiating the hydrocarbon reactant and the supported chromiumcatalyst with a light beam at a wavelength in the UV-visible spectrum toreduce at least a portion of the supported chromium catalyst to form areduced chromium catalyst (e.g., at least a portion of the chromium onthe reduced chromium catalyst can have at least one bonding site with ahydrocarboxy group (—O-hydrocarbon group)); and

(c) hydrolyzing the reduced chromium catalyst to form a reaction productcomprising the alcohol compound and/or the carbonyl compound.

Aspect 2. The process defined in aspect 1, wherein the hydrocarbonreactant comprises a saturated or an unsaturated, linear or branched,aliphatic hydrocarbon, and including combinations thereof.

Aspect 3. The process defined in aspect 1, wherein the hydrocarbonreactant comprises an aromatic compound (e.g., benzene, toluene, xylene,and substituted versions thereof, and including combinations thereof).

Aspect 4. The process defined in aspect 1, wherein the hydrocarbonreactant comprises a linear alkane compound, a branched alkane compound,a cyclic alkane compound, or a combination thereof.

Aspect 5. The process defined in aspect 1, wherein the hydrocarbonreactant comprises a linear olefin compound (e.g., an α-olefin), abranched olefin compound, a cyclic olefin compound, or a combinationthereof.

Aspect 6. The process defined in aspect 1, wherein the hydrocarbonreactant comprises any suitable carbon number alkane compound or anycarbon number alkane compound disclosed herein, e.g., a C₁ to C₃₆ alkanecompound, a C₁ to C₁₈ alkane compound, a C₁ to C₁₂ alkane compound, or aC₁ to C₈ alkane compound; and/or the hydrocarbon reactant comprises anysuitable carbon number olefin compound or any carbon number olefincompound disclosed herein, e.g., a C₂ to C₃₆ olefin compound, a C₂ toC₁₈ olefin compound, a C₂ to C₁₂ olefin compound, or a C₂ to C₈ olefincompound; and/or the hydrocarbon reactant comprises any suitable carbonnumber aromatic compound or any carbon number aromatic compounddisclosed herein, e.g., a C₆ to C₃₆ aromatic compound, a C₆ to C₁₈aromatic compound, a C₆ to C₁₂ aromatic compound, or a C₆ to C₈ aromaticcompound.

Aspect 7. The process defined in aspect 1, wherein the hydrocarbonreactant comprises methane, ethane, propane, butane (e.g., n-butane orisobutane), pentane (e.g., n-pentane, neopentane, or isopentane),hexane, heptane, octane, nonane, decane, undecane, dodecane, tridecane,tetradecane, pentadecane, hexadecane, heptadecane, octadecane, or anycombination thereof; or the hydrocarbon reactant comprises methane,ethane, propane, n-butane, isobutane, n-pentane, neopentane, isopentane,n-hexane, n-heptane, n-octane, n-decane, n-dodecane, or any combinationthereof; or the hydrocarbon reactant comprises methane, ethane, propane,butane, pentane, hexane, or any combination thereof.

Aspect 8. The process defined in aspect 1, wherein the hydrocarbonreactant comprises ethylene, propylene, 1-butene, 1-pentene, 1-hexene,1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene,1-octadecene, cyclopentene, cyclohexene, or any combination thereof.

Aspect 9. The process defined in aspect 1, wherein the hydrocarbonreactant comprises benzene, toluene, ethylbenzene, xylene, mesitylene,or any combination thereof.

Aspect 10. The process defined in aspect 1, wherein the hydrocarbonreactant comprises a C_(n) hydrocarbon compound, the alcohol compoundcomprises a C_(n) alcohol compound, and the carbonyl compound comprisesa C_(n) carbonyl compound.

Aspect 11. The process defined in aspect 10, wherein n is any suitableinteger or an integer in any range disclosed herein, e.g., from 1 to 36,from 1 to 18, from 1 to 12, or from 1 to 8.

Aspect 12. The process defined in aspect 1, wherein the hydrocarbonreactant comprises methane, and the alcohol compound comprises methanol.

Aspect 13. The process defined in any one of the preceding aspects,wherein the supported chromium catalyst and the reduced chromiumcatalyst comprise any suitable amount of chromium or an amount in anyrange disclosed herein, e.g., from about 0.01 to about 50 wt. %, fromabout 0.01 to about 10 wt. %, from about 0.1 to about 15 wt. %, fromabout 0.1 to about 0.5 wt. %, from about 0.2 to about 10 wt. %, fromabout 0.5 to about 2.5 wt. %, from about 2 to about 30 wt. %, or fromabout 3 to about 15 wt. % of chromium, based on the weight of thesupported chromium catalyst or the reduced chromium catalyst.

Aspect 14. The process defined in any one of the preceding aspects,wherein the reduced chromium catalyst comprises any suitable amount ofchromium in an average oxidation state of +5 or less, or an amount inany range disclosed herein, e.g., from about 0.01 to about 50 wt. %,from about 0.01 to about 10 wt. %, from about 0.1 to about 15 wt. %,from about 0.1 to about 0.5 wt. %, from about 0.2 to about 10 wt. %,from about 0.5 to about 2.5 wt. %, from about 2 to about 30 wt. %, orfrom about 3 to about 15 wt. % of chromium in an average oxidation stateof +5 or less, based on the weight of the reduced chromium catalyst.

Aspect 15. The process defined in any one of the preceding aspects,wherein the amount of the chromium of the supported chromium catalyst ina hexavalent oxidation state is at least about 10 wt. %, at least about20 wt. %, at least about 40 wt. %, at least about 60 wt. %, at leastabout 80 wt. %, or at least about 90 wt. %, based on the total amount ofchromium on the supported chromium catalyst, and/or the amount ofchromium of the reduced chromium catalyst in a hexavalent oxidationstate is (from 0 wt. %, from about 0.5 wt. %, from about 1 wt. %, orfrom about 2 wt. % to) less than or equal to about 50 wt. %, less thanor equal to about 40 wt. %, less than or equal to about 30 wt. %, orless than or equal to about 15 wt. %, based on the total amount ofchromium on the reduced chromium catalyst.

Aspect 16. The process defined in any one of the preceding aspects,wherein at least about 10 wt. %, at least about 20 wt. %, at least about40 wt. %, at least about 60 wt. %, at least about 80 wt. %, or at leastabout 90 wt. %, of the supported chromium catalyst is reduced to formthe reduced chromium catalyst, based on the total amount of thesupported chromium catalyst.

Aspect 17. The process defined in any one of the preceding aspects,wherein the chromium in the reduced chromium catalyst has an averagevalence of less than or equal to about 5.25, less than or equal to about5, less than or equal to about 4.75, less than or equal to about 4.5,less than or equal to about 4.25, or less than or equal to about 4.

Aspect 18. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise any suitable solidoxide or any solid oxide disclosed herein, e.g., silica, alumina,silica-alumina, silica-coated alumina, aluminum phosphate,aluminophosphate, heteropolytungstate, titania, zirconia, magnesia,boria, zinc oxide, silica-titania, silica-zirconia, alumina-titania,alumina-zirconia, zinc-aluminate, alumina-boria, alumina borate,silica-boria, aluminophosphate-silica, titania-zirconia, or anycombination thereof.

Aspect 19. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise silica,silica-alumina, silica-coated alumina, silica-titania,silica-titania-magnesia, silica-zirconia, silica-magnesia, silica-boria,aluminophosphate-silica, alumina, alumina borate, or any combinationthereof.

Aspect 20. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise achemically-treated solid oxide comprising a solid oxide (e.g., as inaspect 18 or 19, such as silica, alumina, silica-alumina,silica-titania, silica-zirconia, silica-yttria, aluminophosphate,zirconia, titania, thoria, or stania) treated with anelectron-withdrawing anion.

Aspect 21. The process defined in aspect 20, wherein theelectron-withdrawing anion comprises sulfate, bisulfate, fluoride,chloride, bromide, iodide, fluorosulfate, fluoroborate, phosphate,fluorophosphate, trifluoroacetate, triflate, fluorozirconate,fluorotitanate, phospho-tungstate, tungstate, molybdate, or anycombination thereof.

Aspect 22. The process defined in aspect 20 or 21, wherein thechemically-treated solid oxide contains from about 1 to about 30 wt. %,from about 2 to about 20 wt. %, from about 2 to about 15 wt. %, fromabout 3 to about 12 wt. %, or from 4 to 10 wt. %, of theelectron-withdrawing anion, based on the total weight of thechemically-treated solid oxide.

Aspect 23. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise achemically-treated solid oxide comprising fluorided alumina, chloridedalumina, bromided alumina, sulfated alumina, fluorided silica-alumina,chlorided silica-alumina, bromided silica-alumina, sulfatedsilica-alumina, fluorided silica-zirconia, chlorided silica-zirconia,bromided silica-zirconia, sulfated silica-zirconia, fluoridedsilica-titania, fluorided silica-coated alumina, fluorided-chloridedsilica-coated alumina, sulfated silica-coated alumina, phosphatedsilica-coated alumina, or any combination thereof.

Aspect 24. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the supported chromium catalyst, and thereduced chromium catalyst comprise chromium/silica,chromium/silica-titania, chromium/silica-titania-magnesia,chromium/silica-alumina, chromium/silica-coated alumina,chromium/aluminophosphate, chromium/alumina, chromium/alumina borate, orany combination thereof.

Aspect 25. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the supported chromium catalyst, and thereduced chromium catalyst comprise chromium/silica-titania, and thesupported chromium precursor, the supported chromium catalyst, and thereduced chromium catalyst comprise any suitable amount of titanium or anamount in any range disclosed herein, e.g., from about 0.1 to about 20wt. %, from about 0.5 to about 15 wt. %, from about 1 to about 10 wt. %,or from about 1 to about 6 wt. %, based on the weight of the respectivesupported chromium precursor, supported chromium catalyst, and reducedchromium catalyst.

Aspect 26. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the supported chromium catalyst, and thereduced chromium catalyst comprise chromium/sulfated alumina,chromium/fluorided alumina, chromium/fluorided silica-alumina,chromium/fluorided silica-coated alumina, or any combination thereof.

Aspect 27. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise a zeolite.

Aspect 28. The process defined in aspect 27, wherein the supportedchromium precursor, the solid support, the supported chromium catalyst,and the reduced chromium catalyst comprise a medium pore zeolite, alarge pore zeolite, or a combination thereof.

Aspect 29. The process defined in aspect 27, wherein the zeolitecomprises a ZSM-5 zeolite, a ZSM-11 zeolite, an EU-1 zeolite, a ZSM-23zeolite, a ZSM-57 zeolite, an ALPO4-11 zeolite, an ALPO4-41 zeolite, aFerrierite framework type zeolite, or a combination thereof.

Aspect 30. The process defined in aspect 27, wherein the supportedchromium precursor, the solid support, the supported chromium catalyst,and the reduced chromium catalyst comprise an L-zeolite, a Y-zeolite, amordenite, an omega zeolite, and/or a beta zeolite.

Aspect 31. The process defined in any one of aspects 27-30, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise the zeolite and anysuitable amount of binder or an amount in any range disclosed herein,e.g., from about 3 wt. % to about 35 wt. %, or from about 5 wt. % toabout 30 wt. % binder, based on the weight of the respective supportedchromium precursor, solid support, supported chromium catalyst, andreduced chromium catalyst.

Aspect 32. The process defined in any one of aspects 1-17, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise a clay, anactivated carbon, or a combination thereof.

Aspect 33. The process defined in any one of the preceding aspects,wherein the supported chromium precursor, the solid support, thesupported chromium catalyst, and the reduced chromium catalyst have anysuitable pore volume (total) or a pore volume (total) in any rangedisclosed herein, e.g., from about 0.1 to about 5 mL/g, from about 0.15to about 5 mL/g, from about 0.1 to about 3 mL/g, or from about 0.1 toabout 0.8 mL/g.

Aspect 34. The process defined in any one of the preceding aspects,wherein the supported chromium precursor, the solid support, thesupported chromium catalyst, and the reduced chromium catalyst have anysuitable BET surface area or a BET surface area in any range disclosedherein, e.g., from about 50 to about 2000 m²/g, from about 50 to about700 m²/g, from about 50 to about 400 m²/g, from about 600 to about 1200m²/g, or from about 150 to about 525 m²/g.

Aspect 35. The process defined in any one of the preceding aspects,wherein the supported chromium precursor, the solid support, thesupported chromium catalyst, and the reduced chromium catalyst are inany suitable shape or form or any shape or form disclosed herein, e.g.,powder, round or spherical (e.g., spheres), ellipsoidal, pellet, bead,cylinder, granule (e.g., regular and/or irregular), trilobe, quadralobe,ring, wagonwheel, monolith, or any combination thereof.

Aspect 36. The process defined in any one aspects 1-35, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst have any suitable average(d50) particle size or an average (d50) particle size in any rangedisclosed herein, e.g., from about 10 to about 500 microns, from about25 to about 250 microns, or from about 20 to about 100 microns.

Aspect 37. The process defined in any one aspects 1-35, wherein thesupported chromium precursor, the solid support, the supported chromiumcatalyst, and the reduced chromium catalyst comprise pellets or beadshaving any suitable average size or an average size in any rangedisclosed herein, e.g., from about 1/16 inch to about ½ inch, or fromabout ⅛ inch to about ¼ inch.

Aspect 38. The process defined in any one of aspects 1-37, wherein thewavelength comprises a single wavelength or a range of wavelengths inthe visible spectrum (from 380 nm to 780 nm).

Aspect 39. The process defined in any one of aspects 1-37, wherein thewavelength comprises a single wavelength or a range of wavelengths inthe 200 nm to 750 nm range.

Aspect 40. The process defined in any one of aspects 1-37, wherein thewavelength comprises a single wavelength or a range of wavelengths inthe 300 to 750 nm range, the 350 nm to 650 nm range, the 300 nm to 500nm range, or the 300 nm to 400 nm range.

Aspect 41. The process defined in any one of aspects 1-37, wherein thewavelength comprises a single wavelength or a range of wavelengths below600 nm, below 525 nm, or below 500 nm.

Aspect 42. The process defined in any one of aspects 1-41, wherein thewavelength is a single wavelength.

Aspect 43. The process defined in any one of aspects 1-41, wherein thewavelength is a range of wavelengths spanning at least 25 nm, at least50 nm, at least 100 nm, or at least 200 nm.

Aspect 44. The process defined in any one of the preceding aspects,wherein the light beam has any suitable intensity or an intensity in anyrange disclosed herein, e.g., at least about 500 lumens, at least about1000 lumens, at least about 2000 lumens, at least about 5000 lumens, atleast about 10,000 lumens, or at least about 20,000 lumens.

Aspect 45. The process defined in any one of the preceding aspects,wherein the light beam has any suitable power or any power disclosedherein, e.g., at least about 50 watts, at least about 100 watts, atleast about 200 watts, at least about 500 watts, at least about 1,000watts, or at least about 2,000 watts.

Aspect 46. The process defined in any one of the preceding aspects,wherein the supported chromium catalyst is irradiated with any suitableilluminance or any illuminance disclosed herein, e.g., at least about100 lux, at least about 500 lux, at least about 1000 lux, at least about2000 lux, at least about 5000 lux, at least about 10,000 lux, at leastabout 20,000 lux, or at least about 100,000 lux.

Aspect 47. The process defined in any one of the preceding aspects,wherein the irradiating step is conducted at any suitable temperature orany temperature disclosed herein, e.g., less than about 200° C., lessthan about 100° C., less than about 40° C., from about −100° C. to about100° C., from about 0° C. to about 100° C., or from about 10° C. toabout 40° C.

Aspect 48. The process defined in any one of the preceding aspects,wherein the irradiating step is conducted for any suitable exposure timeor for any exposure time disclosed herein, e.g., from about 15 sec toabout 48 hr, from about 1 min to about 6 hr, from about 1 min to about15 min, or from about 1 hr to about 8 hr.

Aspect 49. The process defined in any one of the preceding aspects,wherein the molar ratio of the hydrocarbon reactant to chromium (of thesupported chromium catalyst) is in any suitable range or any rangedisclosed herein, e.g., at least about 0.25:1, at least about 0.5:1, atleast about 1:1, at least about 10:1, at least about 100:1, at leastabout 1000:1, or at least about 10,000:1.

Aspect 50. The process defined in any one of aspects 1-49, wherein thehydrocarbon reactant is in a gas phase during the irradiating step.

Aspect 51. The process defined in any one of aspects 1-49, wherein thehydrocarbon reactant is in a liquid phase during the irradiating step.

Aspect 52. The process defined in any one of aspects 1-49, wherein theprocess comprises irradiating a slurry of the supported chromiumcatalyst in the hydrocarbon reactant.

Aspect 53. The process defined in any one of aspects 1-49, wherein theprocess comprises contacting the hydrocarbon reactant with a fluidizedbed of the supported chromium catalyst, and irradiating while contacting(fluidizing).

Aspect 54. The process defined in any one of aspects 1-49, wherein theprocess comprises contacting the hydrocarbon reactant (e.g., in a gasphase or in a liquid phase) with a fixed bed of the supported chromiumcatalyst, and irradiating while contacting.

Aspect 55. The process defined in any one of the preceding aspects,wherein the step of irradiating the hydrocarbon reactant with thesupported chromium catalyst is conducted at any suitable WHSV or a WHSVin any range disclosed herein, e.g., from about 0.01 hr⁻¹ to about 500hr⁻¹, or from about 0.1 hr⁻¹ to about 10 hr⁻¹.

Aspect 56. The process defined in any one of the preceding aspects,wherein the hydrolyzing step is conducted at any suitable temperature orany temperature disclosed herein, e.g., less than about 200° C., lessthan about 100° C., less than about 40° C., from about 0° C. to about100° C., or from about 10° C. to about 40° C.

Aspect 57. The process defined in any one of the preceding aspects,wherein the hydrolyzing step comprises contacting the reduced chromiumcatalyst with a hydrolysis agent.

Aspect 58. The process defined in aspect 57, wherein the hydrolysisagent comprises any suitable hydrolysis agent or any hydrolysis agentdisclosed herein, e.g., water, steam, an alcohol agent, an acid agent,an alkaline agent, or any combination thereof.

Aspect 59. The process defined in aspect 58, wherein the hydrolysisagent further comprises any suitable reducing agent or any reducingagent disclosed herein, e.g., ascorbic acid, an iron (II) reducingagent, a zinc reducing agent, or any combination thereof.

Aspect 60. The process defined in any one of the preceding aspects,wherein the carbonyl compound comprises an aldehyde compound, a ketonecompound, an organic acid compound, or any combination thereof.

Aspect 61. The process defined in any one of the preceding aspects,wherein a conversion of the hydrocarbon reactant (or a yield to thealcohol compound, or a yield to the carbonyl compound) is any percentconversion (or yield) disclosed herein, e.g., at least about 2 wt. %, atleast about 5 wt. %, at least about 10 wt. %, or at least about 15 wt. %(and up to about 99 wt. %, about 95 wt. %, about 90 wt. %, about 80 wt.%, about 70 wt. %, or about 50 wt. %).

Aspect 62. The process defined in any one of the preceding aspects,wherein a single pass conversion of the hydrocarbon reactant (or asingle pass yield to the alcohol compound, or a single pass yield to thecarbonyl compound) is any single pass percent conversion (or single passyield) disclosed herein, e.g., at least about 2 wt. %, at least about 5wt. %, at least about 10 wt. %, or at least about 15 wt. % (and up toabout 99 wt. %, about 95 wt. %, about 90 wt. %, about 80 wt. %, about 70wt. %, or about 50 wt. %).

Aspect 63. The process defined in any one of the preceding aspects,wherein the yield to the alcohol compound (or the carbonyl compound) permole of chromium (VI) in the supported chromium catalyst is any molarratio based on moles of chromium (VI) disclosed herein, e.g., at leastabout 0.01, at least about 0.05, at least about 0.1, or at least about0.25 moles (and up to 2, up to about 1.8, up to about 1.6, up to about1.4, up to about 1.2, or up to about 1 mole) of the alcohol compound (orthe carbonyl compound).

Aspect 64. The process defined in any one of the preceding aspects,further comprising a step of separating at least a portion (and in somecases, all) of the hydrocarbon reactant from the reaction product afterstep (c) to produce a separated hydrocarbon portion using any suitabletechnique or any technique disclosed herein, e.g., extraction,filtration, evaporation, distillation, or any combination thereof.

Aspect 65. The process defined in aspect 64, wherein the separatedhydrocarbon portion is recycled and irradiated with the supportedchromium catalyst again.

Aspect 66. The process defined in any one of the preceding aspects,further comprising a step of separating at least a portion (and in somecases, all) of the alcohol compound and/or the carbonyl compound fromthe reaction product using any suitable technique or any techniquedisclosed herein, e.g., extraction, filtration, evaporation,distillation, or any combination thereof.

Aspect 67. The process defined in any one of the preceding aspects,further comprising a step of separating at least a portion (and in somecases, all) of the reduced chromium catalyst from the reaction productafter step (c) to produce a separated reduced chromium catalyst usingany suitable technique or any technique disclosed herein, e.g.,extraction, filtration, evaporation, distillation, or any combinationthereof.

Aspect 68. The process defined in any one of the preceding aspects,further comprising a step of (d) calcining the reduced chromium catalystor the separated reduced chromium catalyst to regenerate the supportedchromium catalyst.

Aspect 69. The process defined in aspect 68, wherein calcining comprisessubjecting the reduced chromium catalyst or the separated reducedchromium catalyst to an oxidizing atmosphere at any suitable calciningtemperature and time conditions or any calcining temperature and timeconditions disclosed herein, e.g., a calcining temperature from about300° C. to about 1000° C., from about 500° C. to about 900° C., or fromabout 550° C. to about 870° C., for a time period of from about 1 min toabout 24 hr, from about 1 hr to about 12 hr, or from about 30 min toabout 8 hr.

Aspect 70. The process defined in any one of aspects 1-69, wherein thepeak temperature in step (a)(i) and (a)(ii) and (a)(iii) is any suitablepeak temperature or any peak temperature disclosed herein, e.g., fromabout 300° C. to about 1000° C., from about 400° C. to about 870° C.,from about 300° C. to about 600° C., from about 100° C. to about 500°C., from about 50° C. to about 400° C., from about 100° C. to about 300°C., or from about 50° C. to about 200° C.

Aspect 71. The process defined in any one of aspects 1-70, wherein step(a)(i) and (a)(ii) and (a)(iii) are conducted in an oxidizingatmosphere.

Aspect 72. The process defined in any one of aspects 1-70, wherein step(a)(i) and (a)(ii) and (a)(iii) are conducted in an inert atmosphere.

Aspect 73. The process defined in any one of aspects 1-72, wherein theprocess comprises step (a)(i), and the supported chromium precursorcomprises any suitable supported chromium precursor or any supportedchromium precursor disclosed herein, e.g., CrO₃ (or anything calcinableto CrO₃), chromium (III) acetate, basic chromium (III) acetate, chromium(III) nitrate, chromium (III) sulfate, chromium (III) chloride (orbromide or iodide), chromium (II) chloride (or bromide or iodide),chromium (III) malate (or propionate, gluconate, or citrate), chromium(III) naphthenate, chromium (III) acetylacetonate (or other diketonate),chromyl chloride, chromium (III) methoxide (or ethoxide or otheralkoxide), chromium (III) 2-ethyl hexanoate (or propionate or othercarboxylate), a chromium (0) compound (e.g., chromium (0) hexacarbonyl,or a diarene chromium (0) compound such as bis-cumene chromium (0),bis-benzene chromium (0), or bis-toluene chromium (0)), a chromium (II)cyclopentadienyl-type compound (e.g., bis-cyclopentadienyl chromium (II)or bis-indenyl chromium (II)), a chromate compound (e.g., potassiumchromate, sodium chromate, ammonium chromate, potassium dichromate,sodium dichromate, or ammonium dichromate), or any combination thereof.

Aspect 74. The process defined in any one of aspects 1-72, wherein theprocess comprises step (a)(i), and the supported chromium precursorcomprises potassium chromate, sodium chromate, ammonium chromate,potassium dichromate, sodium dichromate, ammonium dichromate, or anycombination thereof.

Aspect 75. The process defined in any one of aspects 1-72, wherein theprocess comprises step (a)(ii), and the chromium precursor comprises anysuitable chromium precursor or any chromium precursor disclosed herein,e.g., chromium (III) acetylacetonate, chromium (0), chromyl chloride,chromic oxide (Cr₂O₃), CrO₃, chromium (III) sulfate, chromium (III)nitrate, a chromate compound (e.g., potassium chromate, sodium chromate,ammonium chromate, potassium dichromate, sodium dichromate, or ammoniumdichromate), or any combination thereof.

Aspect 76. The process defined in any one of aspects 1-72, wherein theprocess comprises step (a)(ii), and the chromium precursor comprisespotassium chromate, sodium chromate, ammonium chromate, potassiumdichromate, sodium dichromate, ammonium dichromate, or any combinationthereof.

Aspect 77. The process defined in any one of aspects 1-72, wherein theprocess comprises step (a)(iii), and the chromium precursor comprisesany suitable chromium precursor or any chromium precursor disclosedherein, e.g., CrO₃, bis(t-butyl) chromate (or bis(triphenylsilyl)chromate, or other organic chromium (VI) ester), chromyl chloride, aninorganic chromate compound (e.g., potassium chromate, sodium chromate,ammonium chromate, potassium dichromate, sodium dichromate, or ammoniumdichromate), or any combination thereof.

Aspect 78. A supported catalyst comprising:

a solid support; and

a chromate compound in an amount from about 0.1 to about 25 wt. % ofchromium, based on the weight of the catalyst.

Aspect 79. The catalyst defined in aspect 78, wherein the chromatecompound comprises potassium chromate, sodium chromate, ammoniumchromate, potassium dichromate, sodium dichromate, ammonium dichromate,or any combination thereof.

Aspect 80. A supported catalyst comprising:

a solid support;

from about 0.1 to about 25 wt. % of chromium; and

from about 0.1 to about 25 wt. % of an alkali metal, based on the weightof the catalyst; wherein:

at least one bonding site on the chromium has a ligand characterized bythe following formula: —O-Hydrocarbon group.

Aspect 81. The catalyst defined in aspect 80, wherein the molar ratio ofthe hydrocarbon group to chromium is in any suitable range or any rangedisclosed herein, e.g., from about 0.25:1 to about 2:1, from about 0.5:1to about 2:1, from about 0.5:1 to about 1.5:1, from about 0.75:1 toabout 1.75:1, or from about 0.75:1 to about 1.25:1.

Aspect 82. The catalyst defined in aspect 80 or 81, wherein the catalystcomprises chromium having an average valence of less than or equal toabout 5.25, less than or equal to about 5, less than or equal to about4.75, less than or equal to about 4.5, less than or equal to about 4.25,or less than or equal to about 4.

Aspect 83. The catalyst defined in any one of aspects 80-82, wherein analkoxy group is bonded to the chromium.

Aspect 84. The catalyst defined in any one of aspects 78-83, wherein thesolid support comprises any suitable solid support or any solid supportdisclosed herein, e.g., any support defined in any one of aspects 18-37,such as a solid oxide, a chemically-treated solid oxide, a zeolite, aclay, an activated carbon, or any combination thereof.

Aspect 85. The catalyst defined in any one of aspects 78-84, wherein thesolid support comprises a silica-coated alumina having any suitableweight ratio of alumina to silica or a weight ratio in any rangedisclosed herein, e.g., from 1:20 to about 20:1, from about 1:5 to about5:1, from about 3:1 to about 1:3, from about 1:1 to about 3:1, fromabout 1:1 to about 2:1, or from about 1.2:1 to about 1.8:1.

Aspect 86. The catalyst defined in any one of aspects 78-85, wherein thesupported catalyst comprises any suitable amount of alkali metal or anamount in any range disclosed herein, e.g., from about 0.25 to about 15wt. %, from about 0.5 to about 5 wt. %, from about 2 to about 20 wt. %,or from about 3 to about 15 wt. % of alkali metal, based on the weightof the supported catalyst.

Aspect 87. The catalyst defined in any one of aspects 78-86, wherein thesupported catalyst comprises any suitable amount of chromium or anamount in any range disclosed herein, e.g., from about 0.25 to about 15wt. %, from about 0.5 to about 5 wt. %, from about 2 to about 20 wt. %,or from about 3 to about 15 wt. % of chromium, based on the weight ofthe supported catalyst.

1-20. (canceled)
 21. A process for converting a hydrocarbon reactantinto an alcohol compound and/or a carbonyl compound, the processcomprising: (i) contacting a solid support with an inorganic chromatecompound to form a supported chromium precursor; (ii) heat treating thesupported chromium precursor at a peak temperature from about 50° C. toabout 1000° C. to form a supported chromium catalyst comprising chromiumin a hexavalent oxidation state; (iii) irradiating the hydrocarbonreactant and the supported chromium catalyst with a light beam at awavelength in the UV-visible spectrum to reduce at least a portion ofthe supported chromium catalyst to form a reduced chromium catalyst; and(iv) hydrolyzing the reduced chromium catalyst to form a reactionproduct comprising the alcohol compound and/or the carbonyl compound.22. The process of claim 21, wherein the inorganic chromate compoundcomprises potassium chromate, sodium chromate, ammonium chromate,potassium dichromate, sodium dichromate, ammonium dichromate, or anycombination thereof.
 23. The process of claim 21, wherein step (ii) isconducted in an oxidizing atmosphere.
 24. The process of claim 21,wherein step (ii) is conducted in an inert atmosphere.
 25. The processof claim 21, wherein the peak temperature is in a range from about 100°C. to about 500° C.
 26. The process of claim 21, wherein the peaktemperature is in a range from about 50° C. to about 200° C.
 27. Theprocess of claim 21, wherein the hydrocarbon reactant comprises a C₁ toC₃₆ linear, branched, or cyclic alkane compound.
 28. The process ofclaim 21, wherein the hydrocarbon reactant comprises methane and thealcohol compound comprises methanol.
 29. The process of claim 21,wherein the hydrocarbon reactant comprises a C₂ to C₃₆ olefin compound,a C₆ to C₃₆ aromatic compound, or any combination thereof.
 30. Theprocess of claim 21, wherein: the supported chromium catalyst containsfrom about 0.01 to about 50 wt. % of chromium, based on the weight ofthe supported chromium catalyst; and the reduced chromium catalystcontains chromium having an average valence of less than or equal toabout 5.25.
 31. The process of claim 21, wherein the process comprises:contacting the hydrocarbon reactant with a fluidized bed of thesupported chromium catalyst, and irradiating while contacting; orcontacting the hydrocarbon reactant with a fixed bed of the supportedchromium catalyst, and irradiating while contacting.
 32. The process ofclaim 21, wherein: the hydrocarbon reactant and the supported chromiumcatalyst are irradiated with from about 50,000 to about 500,000 lux ofthe light beam; and the light beam comprises wavelengths above 350 nmand below 500 nm.
 33. The process of claim 21, wherein the solid supportcomprises a solid oxide, a chemically-treated solid oxide, a zeolite, ora combination thereof.
 34. The process of claim 21, wherein: the lightbeam is from a blue light source or a UV light source; the reducedchromium catalyst contains chromium having an average valence of lessthan or equal to about 4.5; and a molar yield of the alcohol compoundand/or the carbonyl compound is from about 0.05 to about 1.8 moles ofthe alcohol compound and/or the carbonyl compound per mole of chromium(VI) in the supported chromium catalyst.
 35. A supported catalystcomprising: a solid oxide comprising silica, silica-titania,silica-titania-magnesia, silica-coated alumina, or any combinationthereof; and a chromate compound in an amount from about 0.1 to about 25wt. % of chromium, based on the weight of the catalyst.
 36. The catalystof claim 35, wherein: the chromate compound comprises potassiumchromate, sodium chromate, ammonium chromate, potassium dichromate,sodium dichromate, ammonium dichromate, or any combination thereof; andthe catalyst contains from about 0.25 to about 15 wt. % chromium. 37.The catalyst of claim 35, wherein the catalyst further comprises fromabout 0.25 to about 15 wt. % alkali metal.
 38. A supported catalystcomprising: a chemically-treated solid oxide comprising sulfatedalumina, fluorided alumina, fluorided silica-alumina, fluoridedsilica-coated alumina, or any combination thereof; and a chromatecompound in an amount from about 0.1 to about 25 wt. % of chromium,based on the weight of the catalyst.
 39. The catalyst of claim 38,wherein: the chromate compound comprises potassium chromate, sodiumchromate, ammonium chromate, potassium dichromate, sodium dichromate,ammonium dichromate, or any combination thereof; and the catalystcontains from about 0.25 to about 15 wt. % chromium.
 40. The catalyst ofclaim 38, wherein the catalyst further comprises from about 0.25 toabout 15 wt. % alkali metal.